Composition and method for controlling pests

ABSTRACT

The present invention provides a composition for controlling pests comprising a compound represented by the formula (1): 
                         
wherein each of symbols are the same as defined in the Description, or N-oxide thereof; and
 
at least one compound selected from the group consisting of neonicotinoid compound, synthetic pyrethroid compound, phenylpyrazole compound, macrolide compound, diamide compound, and insecticidal compound selected from the group consisting of pymetrozine, pyridalyl, pyriproxyfen, spirotetramat, sulfoxaflo and flupyradifurone, which has an excellent control efficacy on pests.

TECHNICAL FIELD

This application claims priority to and the benefit of Japanese Patent Application No. 2013-016594, filed Jan. 31, 2013, the entire contents of which is incorporated herein by reference.

The present invention relates to a composition for controlling pests and a method for controlling pests.

BACKGROUND ART

Hitherto, many compounds have been known as active ingredients in a composition for controlling pests (for example, see Non-Patent Literature-1).

RELATED ART DOCUMENTS Non-Patent Documents

-   [Non-Patent Literature-1]: The Pesticide Manual-15th edition,     published by British Crop Protection Council (BCPC), ISBN     978-=−901396-18-8

SUMMARY OF INVENTION Problems to be Solved by Invention

An object of the present invention is to provide a composition for controlling pests having an excellent control efficacy on pests.

Means to Solve Problems

The present inventors have intensively studied to find out a composition for controlling pests having an excellent control efficacy on pests. As a result, they have found that a composition comprising a compound represented by the following the formula (1) and at least one compound selected from the below-mentioned Group (A) has an excellent controlling effect on pests.

Specifically, the present invention includes:

-   Item 1.

A composition for controlling pests comprising a compound represented by the formula (1) or N-oxide thereof and at least one compound selected from the below-mentioned Group (A);

the formula (1):

wherein

A¹ represents —NR⁷—, an oxygen atom, or a sulfur atom;

A² represents a nitrogen atom or ═CR⁸—;

R¹ represents a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X;

R², R³ and R⁴ are the same or different to each other and each independently represent a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X, a —OR¹⁰ group, a —C(OR¹⁰)₃ group, a —S(O)_(m)R¹⁰ group, a —S(O)₂NR¹⁰R¹¹ group, a —NR¹⁰R¹¹ group, a —NR¹⁰CO₂R¹¹ group, a —NR¹⁰C(O)R¹¹ group, a —CO₂R¹⁰ group, a —C(O)R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, a —SF₅ group, a cyano group, a nitro group, a halogen atom, or a hydrogen atom;

R⁵ and R⁶ are the same or different to each other and each independently represent a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —S(O)₂NR¹⁰R¹¹ group, a —NR¹⁰R¹¹ group, a —NR¹⁰CO₂R¹¹ group, a —NR¹⁰C(O)R¹¹ group, a —CO₂R¹⁰ group, a —C(O)R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, —OC(O)R¹⁰, a —SF₅ group, a —SH group, a cyano group, a nitro group, a halogen atom, or a hydrogen atom, except for a case in which R⁵ and R⁶ are both hydrogen atoms;

R⁷ represents a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group W, a —CO₂R¹⁰ group, a —C(O)R¹⁰ group, a —CH₂CO₂R¹⁰ group, a C3-C6 cycloalkyl group, or a hydrogen atom;

R⁸ represents a C1-C6 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)R¹⁰ group, a cyano group, a nitro group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X or a hydrogen atom, except for a —S(O)_(m)R¹⁰ group wherein m is 1 or 2 and R¹⁰ is a hydrogen atom;

m independently represents 0, 1 or 2; and

n represents 0, 1 or 2;

-   Group X comprising:

a C1-C6 alkoxy group which may be substituted with one or more halogen atoms,

a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms or one or more C1-C3 alkyl groups,

a cyano group,

a hydroxy group, and

a halogen atom;

-   Group W comprising:

a C1-C6 alkoxy group which may be substituted with one or more halogen atoms,

a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms,

a hydroxy group,

a halogen atom, and

a cyano group;

-   at least one compound selected from the below-mentioned Group (A):

group consisting of the following Sub-group A-1, A-2, A-3, A-4, A-5 and A-6:

Sub-group A-1:

-   neonicotinoid compound selected from the group consisting of     imidacloprid, clothianidin thiamethoxam, dinotefuran, acetamiprid,     thiacloprid and nitenpyram;

Sub-group A-2:

-   synthetic pyrethroid compound selected from the group consisting of     acrinathrin, bifenthrin, cycloprothrin, cyfluthrin, beta-cyfluthrin,     cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin,     alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,     zeta-cypermethrin, deltamethrin, etofenprox, fenpropathrin,     fenvalerate, esfenvalerate, flucythrinate, fluvalinate.     tau-fluvalinate, halfenprox, permethrin, silafluofen, tefluthrin,     tralomethrin and protrifenbute;

Sub-group A-3:

-   phenylpyrazole compound selected from the group consisting of     ethiprole, fipronil, acetoprole, vaniliprole, pyriprole and     pyrafluprole;

Sub-group A-4:

-   macrolide compound selected from the group consisting of abamectin,     emamectin, emamectin benzoate, milbemectine, doramectin and     lepimectin;

Sub-group A-5:

-   diamide compound selected from the group consisting of flubendiamide     and the compound represented by formula (2):

[wherein,

R¹ represents a methyl group or a bromine group,

R² represents a bromine atom, a chlorine atom or a cyano group,

R³ represents a methyl group, a 1-cyclopropylmethyl group or a methoxycarbonylamino group, and

R⁴ represents a hydrogen atom or an ethyl group]

Sub-group A-6:

-   insecticidal compound selected from the group consisting of     pymetrozine, pyridalyl, pyriproxyfen, spirotetramat, sulfoxaflo and     flupyradifurone. -   Item 2.

The composition for controlling pests according to Item 1, wherein in the compound represented by the formula (1) or N-oxide thereof,

R¹ is a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group Y;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —CO₂R¹⁰ group, a —SF₅ group, or a halogen atom;

R⁶ is a —OR¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, —OC(O)R¹⁰, a cyano group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms, a —CH₂CO₂R¹⁰ group, a C3-C6 cycloalkyl group, or a hydrogen atom,

R⁸ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms or a hydrogen atom, except for a —S(O)_(m)R¹⁰ group wherein m is 1 or 2 and R¹⁰ is a hydrogen atom; and

Group Y comprising:

a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms and

a halogen atom.

-   Item 3.

The composition for controlling pests according to Item 1, wherein in the compound represented by the formula (1) or N-oxide thereof,

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; and

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms.

-   Item 4.

The composition for controlling pests according to Item 1, wherein in the compound represented by the formula (1) or N-oxide thereof:

R¹ is an ethyl group;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 haloalkyl group, a —OR²⁰ group, a —S(O)_(m)R²⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; and

R²⁰ is a C1-C3 haloalkyl group.

-   Item 5.

The composition for controlling pests according to any one of Items 1 to 4, wherein in the compound represented by the formula (1) or N-oxide thereof,

A¹ is —NR⁷—.

-   Item 6.

The composition for controlling pests according to any one of Items 1 to 4, wherein in the compound represented by the formula (1) or N-oxide thereof,

A¹ is an oxygen atom.

-   Item 7.

The composition for controlling pests according to any one of Items 1 to 4, wherein in the compound represented by the formula (1) or N-oxide thereof,

A¹ is a sulfur atom.

-   Item 8.

The composition for controlling pests according to Item 1, wherein the compound represented by the formula (1) or N-oxide thereof is a compound represented by the formula (1-2) or N-oxide thereof;

the formula (1-2):

wherein

R^(1a) represents a C1-C3 alkyl group;

A^(2a) represents a nitrogen atom or ═CR^(8a)—;

R^(3a) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10a))₃ group, a halogen atom, or a hydrogen atom;

R^(5a) represents a C1-C3 haloalkyl group, a —OR^(20a) group, a —S(O)_(m)R^(20a) group, or a halogen atom;

R^(6a) represents a cyano group, a —NR¹⁰R^(11a) group, a halogen atom, or a hydrogen atom;

R^(7a) represents a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R^(8a) represents a —S(O)_(m)R^(10a) group, a cyano group, a halogen atom, or a hydrogen atom;

R^(10a) and R^(11a) are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R^(20a) represents a C1-C3 haloalkyl group;

m independently represents 0, 1 or 2; and

n represents 0, 1 or 2.

-   Item 9.

The composition for controlling pests according to Item 1, wherein the compound represented by the formula (1) or N-oxide thereof is a compound represented by the formula (1-3) or N-oxide thereof;

the formula (1-3):

wherein

A^(2b) represents a nitrogen atom or ═CR^(8b)—;

R^(3b) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10b))₃ group, a halogen atom, or a hydrogen atom;

R^(5b) represents a C1-C3 haloalkyl group, a —OR^(20b) group, a —S(O)_(m)R^(20b) group, or a halogen atom;

R^(8b) represents a —S(O)_(m)R^(10b) group, a cyano group, a halogen atom, or a hydrogen atom;

R^(10b) independently represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R^(20b) represents a C1-C3 haloalkyl group;

m independently represents 0, 1 or 2; and

n represents 0, 1 or 2.

-   Item 10.

The composition for controlling pests according to Item 9, wherein in the compound represented by the formula (1-3) or N-oxide thereof,

R^(3b) is a halogen atom or a hydrogen atom;

R^(5b) is a C1-C3 perfluoroalkyl group, a —OR^(30b) group, or a —S(O)_(m)R^(30b) group;

R^(30b) is a C1-C3 perfluoroalkyl group; and

R^(8b) is a halogen atom or a hydrogen atom.

-   Item 11.

The composition for controlling pests according to Item 1, wherein the compound represented by the formula (1) or N-oxide thereof is a compound represented by the formula (1-4) or N-oxide thereof;

the formula (1-4):

wherein

A^(2c) represents a nitrogen atom or ═CR^(8c)—;

R^(3c) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10c))₃ group, a halogen atom, or a hydrogen atom;

R^(5c) represents a C1-C3 haloalkyl group, a —OR^(20c) group, a —S(O)_(m)R^(20c) group, or a halogen atom;

R^(8c) represents a —S(O)_(m)R^(10c) group, a cyano group, a halogen atom, or a hydrogen atom;

R^(10c) independently represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R^(20c) represents a C1-C3 haloalkyl group;

m independently represents 0, 1 or 2; and

n represents 0, 1 or 2.

-   Item 12.

The composition for controlling pests according to Item 11, wherein in the compound represented by the formula (1-4) or N-oxide thereof,

R^(3c) is a halogen atom or a hydrogen atom;

R^(5c) is a C1-C3 perfluoroalkyl group, a —OR^(30c) group, or a —S(O)_(m)R^(30c) group,

R^(30c) is a C1-C3 perfluoroalkyl group, and

R^(8c) is a halogen atom or a hydrogen atom.

-   Item 13.

The composition for controlling pests according to any one of Items 1 to 7 wherein a weight ratio of the compound represented by the formula (1) to at least one compound selected from the above-mentioned Group (A) is in a range of 100:1 to 1:100.

-   Item 14.

The composition for controlling pests according to any one of Items 1 to 7 wherein a weight ratio of the compound represented by the formula (1) to at least one compound selected from the above-mentioned Group (A) is in a range of 10:1 to 1:10.

-   Item 15.

The composition for controlling pests according to Item 8 wherein a weight ratio of the compound represented by the formula (1-2) to at least one compound selected from the above-mentioned Group (A) is in a range of 100:1 to 1:100.

-   Item 16.

The composition for controlling pests according to Item 8 wherein a weight ratio of the compound represented by the formula (1-2) to at least one compound selected from the above-mentioned Group (A) is in a range of 10:1 to 1:10.

-   Item 17.

The composition for controlling pests according to Item 9 or 10 wherein a weight ratio of the compound represented by the formula (1-3) to at least one compound selected from the above-mentioned Group (A) is in a range of 100:1 to 1:100.

-   Item 18.

The composition for controlling pests according to Item 9 or 10 wherein a weight ratio of the compound represented by the formula (1-3) to at least one compound selected from the above-mentioned Group (A) is in a range of 10:1 to 1:10.

-   Item 19.

The composition for controlling pests according to Item 11 or 12 wherein a weight ratio of the compound represented by the formula (1-4) to at least one compound selected from the above-mentioned Group (A) is in a range of 100:1 to 1:100.

-   Item 20.

The composition for controlling pests according to Item 11 or 12 wherein a weight ratio of the compound represented by the formula (1-4) to at least one compound selected from the above-mentioned Group (A) is in a range of 10:1 to 1:10.

-   Item 21.

A method for controlling pests, which comprises the step of applying an effective amount of the composition for controlling pests according to any one of Items 1 to 20 to pests or a habitat where pests live.

-   Item 22.

A method for controlling pests, which comprises the step of applying an effective amount of the composition for controlling pests according to any one of Items 1 to 20 to plants, plant seeds, bulbs, or a soil where plants grow.

The present invention can control pests.

MODE FOR CARRYING OUT THE INVENTION

A composition for controlling pests of the present invention comprises the compound represented by the formula (1) (hereinafter referred to as “(the) present fused heterocyclic compound”) and at least one compound selected from the above-mentioned Group (A) (hereinafter referred to as “insecticidal compound”).

For the present fused heterocyclic compound, “N-oxide” includes a compound wherein one or more ring-constituting nitrogen atoms in one or more the heterocyclic moieties are oxidized. The heterocyclic moieties which may form N-oxide includes, for example, the pyridine ring moiety.

For example, the nitrogen atom of the pyridine ring moiety of the formula (1) may be N-oxide (N→O).

Further, for example, in the formula (1), A² may be N-oxide (N→O).

The examples of each group as used herein are explained as follows.

In the following “Ca-Cb”, “a” means the smallest number of the carbon atoms and “b” means the largest number of carbon atoms.

The term “Ca-Cb alkyl group” as used herein represents a straight- or branched-chain hydrocarbon group having “a” to “b” carbon atoms.

The term “Ca-Cb haloalkyl group represents a straight- or branched-chain hydrocarbon group having “a” to “b” carbon atoms, wherein one or more hydrogen atoms attached to the carbon atoms are replaced with one or more halogen atoms. When two or more halogen atoms are attached to the carbon atoms, the halogen atoms may be the same or different.

The term “Ca-Cb alkoxy group” represents a straight- or branched-chain alkyl-O— group having “a” to “b” carbon atoms.

The term “Ca-Cb cycloalkyl group” represents a saturated cyclic hydrocarbon group having “a” to “b” carbon atoms.

In “which may be substituted with one or more atoms or groups selected from Group X” as used herein, when substituted with two or more atoms or groups selected from Group X, the atoms or groups selected from Group X may be the same or different to each other.

In “which may be substituted with one or more atoms or groups selected from Group Y” as used herein, when substituted with two or more atoms or groups selected from Group Y, the atoms or groups selected from Group Y may be the same or different to each other.

In “which may be substituted with one or more atoms or groups selected from Group W” as used herein, when substituted with two or more atoms or groups selected from Group W, the atoms or groups selected from Group V may be the same or different to each other.

In “which may be substituted with one or more halogen atoms” as used herein, when substituted with two or more halogen atoms, the halogen atoms may be the same or different to each other.

In “which may be substituted with one or more C1-C3 alkyl groups” as used herein, when substituted with two or more C1-C3 alkyl groups, the C1-C3 alkyl groups may be the same or different to each other.

In the present fused heterocyclic compound, the term “halogen atom” includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the present fused heterocyclic compound, “a C1-C6 alkyl group which may be substituted with one or more (for example, 1 to 7, 1 to 5, or 1 to 3) atoms or groups selected from Group X” represents a straight- or branched-chain saturated hydrocarbon group having 1 to 6 carbon atoms, wherein one or more hydrogen atoms attached to the carbon atoms may optionally be replaced with one or more atoms or groups selected from Group X. When substituted with two or more atoms or groups selected from Group X, the atoms or groups selected from Group X may be the same or different to each other.

Examples of “a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, methoxymethyl group, ethoxymethyl group, propyloxymethyl group, isopropyloxymethyl group, butyloxymethyl group, sec-butyloxymethyl group, tert-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propyloxyethyl group, 2-isopropyloxyethyl group, 2-butyloxyethyl group, 2-sec-butyloxyethyl group, 2-tert-butyloxyethyl group, trifluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group and pentafluoroethyl group, 2-hydroxyethyl group, cyclopropylmethyl group, 1-methylcyclopropylmethyl group, 2,2-difluorocyclopropylmethyl group, trimethoxymethyl group, triethoxymethyl group etc. Examples of subgroups such as “a C1-C3 alkyl group which may be substituted with one or more atoms or groups selected from Group X” may be selected from the above, depending on the indicated number of carbon atom.

In the present fused heterocyclic compound, “a C1-C6 alkyl group which may be substituted with one or more (for example, 1 to 7, 1 to 5, or 1 to 3) halogen atoms” represents a straight- or branched-chain hydrocarbon group having 1 to 6 carbon atoms, wherein one or more hydrogen atoms attached to the carbon atoms may optionally be replaced with one or more halogen atoms. When substituted with two or more halogen atoms, the halogen atoms may be the same or different to each other.

Examples of “a C1-C6 alkyl group which may be substituted with one or more halogen atoms” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, trifluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, and pentafluoroethyl group, heptafluoroisopropyl group etc. Examples of subgroups such as “a C1-C3 alkyl group which may be substituted with one or more halogen atoms” may be selected from the above, depending on the indicated number of carbon atom.

In the present fused heterocyclic compound, examples of “a C1-C6 alkyl group which may be substituted with one or more (for example, 1 to 7, 1 to 5, or 1 to 3) atoms or groups selected from Group W” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, trifluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, methoxymethyl group, ethoxymethyl group, propyloxymethyl group, isopropyloxymethyl group, butyloxymethyl group, sec-butyloxymethyl group, isobutyloxymethyl group, tert-butyloxymethyl group, methoxyethyl group, ethoxyethyl group, propyloxyethyl group, isopropyloxyethyl group, butyloxyethyl group, sec-butyloxyethyl group, isobutyloxyethyl group, tert-butyloxyethyl group etc. When substituted with two or more atoms or groups selected from Group W, the atoms or groups selected from Group W may be the same or different to each other.

In the present fused heterocyclic compound, examples of “a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group Y” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, trifluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group and pentafluoroethyl group, cyclopropylmethyl group, 1-methylcyclopropylmethyl group, 2,2-difluorocyclopropylmethyl group etc. Examples of subgroups are selected from the above, depending on the indicated number of carbon atom.

In the present fused heterocyclic compound, examples of “a C1-C6 alkoxy group which may be substituted with one or more (for example, 1 to 7, 1 to 5, or 1 to 3) halogen atoms” includes methoxy group, trifluoromethoxy group, ethoxy group, 2,2,2-trifluoroethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, pentyloxy group, and hexyloxy group.

In the present fused heterocyclic compound, examples of “a C3-C6 cycloalkyl group which may be substituted with one or more (for example, 1 to 7, 1 to 5, or 1 to 3) halogen atoms” include cyclopropyl group, 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

In the present fused heterocyclic compound, examples of “a C3-C6 cycloalkyl group which may be substituted with one or more (for example, 1 to 7, 1 to 5, or 1 to 3) halogen atoms or one or more (for example, 1 to 7, 1 to 5, or 1 to 3) C1-C3 alkyl groups” include cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 1-fluorocyclopropyl group, 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

In the present fused heterocyclic compound, the term “a C1-C3 haloalkyl group” represents a straight- or branched-chain hydrocarbon group having 1 to 3 carbon atoms, wherein one or more hydrogen atoms attached to the carbon atoms are replaced with one or more (for example, 1 to 7, 1 to 5, or 1 to 3) halogen atoms. When substituted with two or more halogen atoms, the halogen atoms may be the same or different to each other.

Examples of “a C1-C3 haloalkyl group” include fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group etc.

In the present fused heterocyclic compound, examples of “C1-C3 alkyl group” include methyl group, ethyl group, propyl group, and isopropyl group.

In the present fused heterocyclic compound, examples of “C1-C3 perfluoroalkyl group” include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, and heptafluoroisopropyl group.

Examples of the present fused heterocyclic compound include as follows.

The compound represented by the formula (1), wherein

R¹ is a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group Y;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —CO₂R¹⁰ group, a —SF₅ group, or a halogen atom;

R⁶ is a —OR¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, —OC(O)R¹⁰, a cyano group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms, a —CH₂CO₂R¹⁰ group, a C3-C6 cycloalkyl group, or a hydrogen atom;

R⁸ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms or a hydrogen atom, except for a —S(O)_(m)R¹⁰ group wherein m is 1 or 2 and R¹⁰ is a hydrogen atom; and

Group Y comprising:

a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms and

a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; and

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; or N-oxide thereof.

The compound represented by the formula (1), wherein

R¹ is an ethyl group;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 haloalkyl group, a —OR²⁰ group, a —S(O)_(m)R²⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; and

R²⁰ is a C1-C3 haloalkyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is —NR⁷—; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is —NR⁷—;

R¹ is a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group Y;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —CO₂R¹⁰ group, a —SF₅ group, or a halogen atom;

R⁶ is a —OR¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, —OC(O)R¹⁰, a cyano group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms, a —CH₂CO₂R¹⁰ group, a C3-C6 cycloalkyl group, or a hydrogen atom;

R⁸ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms or a hydrogen atom, except for a —S(O)_(m)R¹⁰ group wherein m is 1 or 2 and R¹⁰ is a hydrogen atom; and

Group Y comprising:

a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms, and

a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is —NR⁷—;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; and

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is —NR⁷—;

R¹ is an ethyl group;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 haloalkyl group, a —OR²⁰ group, a —S(O)_(m)R²⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom,

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; and

R²⁰ is a C1-C3 haloalkyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is an oxygen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is an oxygen atom;

R¹ is a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group Y;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —CO₂R¹⁰ group, a —SF₅ group, or a halogen atom;

R⁶ is a —OR¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, —OC(O)R¹⁰, a cyano group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms, a —CH₂CO₂R¹⁰ group, a C3-C6 cycloalkyl group, or a hydrogen atom;

R⁸ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms or a hydrogen atom, except for a —S(O)_(m)R¹⁰ group wherein m is 1 or 2 and R¹⁰ is a hydrogen atom; and

Group Y comprising:

a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms, and

a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is an oxygen atom;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; and

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is a sulfur atom;

R¹ is an ethyl group;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 haloalkyl group, a —OR²⁰ group, a —S(O)_(m)R¹⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; and

R²⁰ is a C1-C3 haloalkyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is a sulfur atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is a sulfur atom;

R¹ is a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group Y;

R² and R⁴ are hydrogen atoms,

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —CO₂R¹⁰ group, a —SF₅ group, or a halogen atom;

R⁶ is a —OR¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, —OC(O)R¹⁰, a cyano group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms, a —CH₂CO₂R¹⁰ group, a C3-C6 cycloalkyl group, or a hydrogen atom;

R⁸ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms or a hydrogen atom, except for a —S(O)_(m)R¹⁰ group wherein m is 1 or 2 and R¹⁰ is a hydrogen atom; and

Group Y comprising:

a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms, and

a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is a sulfur atom;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; and

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is a sulfur atom;

R¹ is an ethyl group;

R² and R⁴ are hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰) group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 haloalkyl group, a —OR²⁰ group, a —S(O)_(m)R²⁰ group, or a halogen atom;

R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom;

R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom;

R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; and

R²⁰ is a C1-C3 haloalkyl group; or N-oxide thereof.

The compound represented by the formula (1-2):

wherein

R^(1a) represents a C1-C3 alkyl group;

A^(2a) represents a nitrogen atom or ═CR^(8a)—;

R^(3a) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10a))₃ group, a halogen atom, or a hydrogen atom;

R^(5a) represents a C1-C3 haloalkyl group, a —OR^(20a) group, a —S(O)_(m)R^(20a) group, or a halogen atom;

R^(6a) represents a cyano group, a —NR^(10a)R^(11a) group, a halogen atom, or a hydrogen atom;

R^(7a) represents a C1-C6 alkyl group which may be substituted with one or more halogen atoms;

R^(8a) represents a —S(O)_(m)R^(10a) group, a cyano group, a halogen atom, or a hydrogen atom;

R^(10a) and R^(11a) are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R^(20a) represents a C1-C3 haloalkyl group;

m independently represents 0, 1 or 2; and

n represents 0, 1 or 2; or N-oxide thereof.

The compound represented by the formula (1-3):

wherein

A^(2b) represents a nitrogen atom or ═CR^(8b)—;

R^(3b) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10b))₃ group, a halogen atom, or a hydrogen atom;

R^(5b) represents a C1-C3 haloalkyl group, a —OR^(20b) group, a —S(O)_(m)R^(20b) group, or a halogen atom;

R^(8b) represents a —S(O)_(m)R^(10b) group, a cyano group, a halogen atom, or a hydrogen atom;

R^(10b) independently represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R^(20b) represents a C1-C3 haloalkyl group;

m independently represents 0, 1 or 2; and

n represents 0, 1 or 2; or N-oxide thereof.

The compound represented by the formula (1-3), wherein

R^(3b) is a halogen atom or a hydrogen atom;

R^(5b) is a C1-C3 perfluoroalkyl group, a —OR^(30b) group, or a —S(O)_(m)R^(30b) group;

R^(30b) is a C1-C3 perfluoroalkyl group; and

R^(8b) is a halogen atom or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-4):

wherein

A^(2c) represents a nitrogen atom or ═CR^(8c)—;

R^(3c) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10c))₃ group, a halogen atom, or a hydrogen atom;

R^(5c) represents a C1-C3 haloalkyl group, a —OR^(20c) group, a —S(O)mR^(20c) group, or a halogen atom;

R^(8c) represents a —S(O)_(m)R^(10c) group, a cyano group, a halogen atom, or a hydrogen atom;

R^(10c) independently represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R^(20c) represents a C1-C3 haloalkyl group;

m independently represents 0, 1 or 2; and

n represents 0, 1 or 2; or N-oxide thereof.

The compound represented by the formula (1-4), wherein

R^(3c) is a halogen atom or a hydrogen atom;

R^(5c) is a C1-C3 perfluoroalkyl group, a —OR^(30c) group, or a —S(O)_(m)R^(30c) group;

R^(30c) is a C1-C3 perfluoroalkyl group; and

R^(8c) is a halogen atom or a hydrogen atom; or N-oxide thereof.

Formula (1):

The compound represented by the formula (1), wherein A¹ is —NR⁷—, and R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms, or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is —NR⁷—, and R⁷ is a methyl group, an ethyl group, or a propyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is —NR⁷—, and R⁷ is a methyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is —NR⁷—, and R⁷ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein A² is a nitrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein A² is ═N(→O)—: (N-oxide).

The compound represented by the formula (1), wherein A² is ═CR⁸—; or N-oxide thereof.

The compound represented by the formula (1), wherein A² is ═CR⁸—, and R⁸ is a C1-C3 alkoxy group, a C1-C3 alkylsulfonyl group, a halogen atom, or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein A² is ═CR⁸—, and R⁸ is a C1-C3 alkoxy group; or N-oxide thereof.

The compound represented by the formula (1), wherein A² is ═CR⁸—, and R⁸ is a C1-C3 alkylsulfonyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein A² is ═CR⁸—, and R⁸ is a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein A² is ═CH—; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is —NR⁷—, and A² is a nitrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is —NR⁷—, and A² is ═N(→O)—: (N-oxide).

The compound represented by the formula (1), wherein A¹ is —NR⁷—, and A² is ═CR⁸—; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is —NR⁷—, and A² is ═CH—; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is an oxygen atom, and A² is a nitrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is an oxygen atom, and A² is ═N(→O)—: (N-oxide).

The compound represented by the formula (1), wherein A¹ is an oxygen atom, and A² is ═CR⁸—; or N-oxide thereof.

The compound represented by the formula (1), wherein A is an oxygen atom, and A² is —CH—; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is a sulfur atom, and A² is a nitrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is a sulfur atom, and A² is ═N(→O)—: (N-oxide).

The compound represented by the formula (1), wherein A¹ is a sulfur atom, and A² is ═CR⁸—; or N-oxide thereof.

The compound represented by the formula (1), wherein A¹ is a sulfur atom, and A² is ═CH—; or N-oxide thereof.

The compound represented by the formula (1), wherein R¹ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms or a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms; or N-oxide thereof.

The compound represented by the formula (1), wherein R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms; or N-oxide thereof.

The compound represented by the formula (1), wherein R¹ is a methyl group, an ethyl group, or a propyl group, an isopropyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a cyclopropyl group, or a cyclopropylmethyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R¹ is an ethyl group or a cyclopropylmethyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R¹ is a methyl group; or N-oxide thereof;

The compound represented by the formula (1), wherein R¹ is an ethyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R¹ is a propyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R¹ is an isopropyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X, a halogen atom, or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a —C(OR¹⁰)₃ group; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a methyl group, a trifluoromethyl group, a pentafluoroethyl group, a hexafluoropropyl group, a hexafluoroisopropyl group, a trimethoxymethyl group, a triethoxymethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a trifluoromethyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R³ is a trimethoxymethyl group, or N-oxide thereof;

The compound represented by the formula (1), wherein R² and R⁴ are both hydrogen atoms; or N-oxide thereof.

The compound represented by the formula (1), wherein R² and R⁴ are both hydrogen atoms, and R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R² and R⁴ are both hydrogen atoms, and R³ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R² and R⁴ are both hydrogen atoms, and R³ is a trifluoromethyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R² and R⁴ are both hydrogen atoms, and R³ is a trimethoxymethyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —CO₂R¹⁰ group, a —SF₅ group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group, a C1-C3 haloalkylsulfanyl group, a C1-C3 haloalkylsulfinyl group, a C1-C3 haloalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 perfluoroalkyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 perfluoroalkoxy group; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, or a C1-C3 perfluoroalkylsulfonyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a halogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a trifluoromethyl group, —CF₂CF₃, —CF₂CF₂CF₃, —CF(CF₃)₂, —OCF₃, —OCF₂CF₃, —SCF₃, —S(O)CF₃, —S(O)₂CF₃, —SCF₂CF₃, —S(O)CF₂CF₃, —S(O)₂CF₂CF₃, —SF₅, a fluorine atom, a chlorine atom, a bromine atom, or a iodine atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a trifluoromethyl group; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is —CF₂CF₃; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is —SCF₃; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is —S(O)CF₃; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is —S(O)₂CF₃; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁶ is a —OR¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)NR¹⁰R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group, a C1-C3 haloalkylsulfanyl group, a C1-C3 haloalkylsulfinyl group, a C1-C3 haloalkylsulfonyl group, or a halogen atom, and R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom, and R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 perfluoroalkyl group, and R¹ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 perfluoroalkoxy group, and R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein R⁵ is a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, or a C1-C3 perfluoroalkylsulfonyl group, and R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is —NR⁷—;

R⁷ is a methyl group;

A² is a nitrogen atom;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are both hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom, and

R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is —NR⁷—;

R⁷ is a methyl group;

A² is —N(→O)—;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are both hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; and

R⁶ is a hydrogen atom; (N-oxide).

The compound represented by the formula (1), wherein

A¹ is —NR⁷—;

R⁷ is a methyl group;

A² is ═CR⁸—;

R⁸ is a C1-C3 alkoxy group, a C1-C3 alkylsulfanyl group, a halogen atom, or a hydrogen atom;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are both hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom, and

R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is an oxygen atom;

A² is a nitrogen atom;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are both hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom, and

R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1), wherein

A¹ is an oxygen atom;

A² is ═N(→O)—;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are both hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom, and

R⁶ is a hydrogen atom (N-oxide).

The compound represented by the formula (1), wherein

A¹ is an oxygen atom;

A² is ═CR⁸—;

R⁸ is a C1-C3 alkoxy group, a C1-C3 alkylsulfanyl group, a halogen atom, or a hydrogen atom;

R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms;

R² and R⁴ are both hydrogen atoms;

R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom;

R⁵ is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; and

R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein A^(2a) is a nitrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein A^(2a) is ═N(→O)—: (N-oxide).

The compound represented by the formula (1-2), wherein A^(2a) is ═CR^(8a)—; or N-oxide thereof.

The compound represented by the formula (1-2), wherein A^(2a) is ═CH—; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(1a) is a methyl group; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(1a) is an ethyl group; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(1a) is a propyl group; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(1a) is an isopropyl group; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(3a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(3a) is a trifluoromethyl group; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(5a) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom, and R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(5a) is a trifluoromethyl group, and R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(5a) is —CF₂CF₃, and R⁶ is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(5a) is —SCF₃, and R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(5a) is —S(O)CF₃, and R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein R^(5a) is —S(O)₂CF₃, and R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein

A^(2a) is a nitrogen atom;

R^(1a) is an ethyl group;

R^(3a) is a hydrogen atom;

R^(5a) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; and

R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein

A^(2a) is ═N(→O)—;

R^(1a) is an ethyl group;

R^(3a) is a hydrogen atom;

R^(5a) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; and

R^(6a) is a hydrogen atom: (N-oxide).

The compound represented by the formula (1-2), wherein

A^(2a) is ═CR^(8a)—;

R^(1a) is a C1-C3 alkoxy group, a C1-C3 alkylsulfanyl group, a halogen atom, or a hydrogen atom;

R^(1a) is an ethyl group;

R^(3a) is a hydrogen atom;

R^(5a) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; and

R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein

A^(2a) is a nitrogen atom;

R^(1a) is an ethyl group;

R^(3a) is a trifluoromethyl group;

R^(5a) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; and

R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-2), wherein

A^(2a) is ═N(→O)—;

R^(1a) is an ethyl group;

R^(3a) is a trifluoromethyl group;

R^(5a) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom, and

R^(6a) is a hydrogen atom: (N-oxide).

The compound represented by the formula (1-2), wherein

A^(2a) is ═CR^(8a)—;

R⁸ is a C1-C3 alkoxy group, a C1-C3 alkylsulfanyl group, a halogen atom, or a hydrogen atom;

R^(1a) is an ethyl group;

R^(3a) is a trifluoromethyl group;

R^(5a) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; and

R^(6a) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-3), wherein A^(2b) is a nitrogen atom; or N-oxide thereof.

The compound represented by the formula (1-3), wherein A^(2b) is ═N(→O)—: (N-oxide).

The compound represented by the formula (1-3), wherein A^(2b) is ═CR^(8b)—; or N-oxide thereof.

The compound represented by the formula (1-3), wherein A^(2b) is ═CH—; or N-oxide thereof.

The compound represented by the formula (1-3), wherein R^(3b) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-3), wherein R^(3b) is a trifluoromethyl group; or N-oxide thereof.

The compound represented by the formula (1-3), wherein R^(5b) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1-3), wherein R^(5b) is a trifluoromethyl group; or N-oxide thereof.

The compound represented by the formula (1-3), wherein R^(5b) is —CF₂CF₃; or N-oxide thereof.

The compound represented by the formula (1-3), wherein R^(5b) is —SCF₃; or N-oxide thereof.

The compound represented by the formula (1-3), wherein R^(5b) is —S(O)CF₃; or N-oxide thereof.

The compound represented by the formula (1-3), wherein R^(5b) is —S(O)₂CF₃; or N-oxide thereof.

The compound represented by the formula (1-3), wherein

A^(2b) is a nitrogen atom;

R^(3b) is a hydrogen atom;

R^(5b) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1-3), wherein

A^(2b) is ═N(→O)—;

R^(3b) is a hydrogen atom; and

R^(5b) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom: (N-oxide).

The compound represented by the formula (1-3), wherein

A^(2b) is ═CR^(8b)—;

R⁸ is a C1-C3 alkoxy group, a C1-C3 alkylsulfanyl group, a halogen atom, or a hydrogen atom;

R^(3b) is a hydrogen atom;

R^(5b) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1-3), wherein

A^(2b) is a nitrogen atom;

R^(3b) is a trifluoromethyl group;

R^(5b) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylaulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylaulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1-3), wherein

A^(2b) is —N(→O)—;

R^(3b) is a trifluoromethyl group;

R^(5b) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylaulfonyl group, or a halogen atom; (N-oxide)

The compound represented by the formula (1-3), wherein

A^(2b) is ═CR^(8b)—;

R⁸ is a C1-C3 alkoxy group, a C1-C3 alkylsulfanyl group, a halogen atom, or a hydrogen atom;

R^(3b) is a trifluoromethyl group;

R^(5b) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1-4), wherein A^(2c) is a nitrogen atom; or N-oxide thereof.

The compound represented by the formula (1-4), wherein A^(2c) is ═N(→O)—: (N-oxide).

The compound represented by the formula (1-4), wherein A^(2c) is ═CR^(8c)—; or N-oxide thereof.

The compound represented by the formula (1-4), wherein A^(2c) is ═CH—; or N-oxide thereof.

The compound represented by the formula (1-4), wherein R^(3c) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-4), wherein R^(3c) is a trifluoromethyl group; or N-oxide thereof.

The compound represented by the formula (1-4), wherein R^(5c) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom, and R^(6c) is a hydrogen atom; or N-oxide thereof.

The compound represented by the formula (1-4), wherein R^(5c) is a trifluoromethyl group; or N-oxide thereof.

The compound represented by the formula (1-4), wherein R^(5c) is —CF₂CF₃; or N-oxide thereof.

The compound represented by the formula (1-4), wherein R^(5c) is —SCF₃; or N-oxide thereof.

The compound represented by the formula (1-4), wherein R^(5c) is —S(O)CF₃; or N-oxide thereof.

The compound represented by the formula (1-4), wherein R^(5c) is —S(O)₂CF₃, or N-oxide thereof.

The compound represented by the formula (1-4), wherein

A²C is a nitrogen atom;

R^(3c) is a hydrogen atom;

R^(5c) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1-4), wherein

A^(2c) is ═N(→O)—;

R^(3c) is a hydrogen atom; and

R^(5c) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom: (N-oxide).

The compound represented by the formula (1-4), wherein

A^(2c) is ═CR^(8c)—;

R⁸ is a C1-C3 alkoxy group, C1-C3 alkylsulfanyl group, a halogen atom, or a hydrogen atom;

R^(3c) is a hydrogen atom;

R^(5c) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1-4), wherein

A^(2c) is a nitrogen atom;

R^(3c) is a trifluoromethyl group; and

R^(5c) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

The compound represented by the formula (1-4), wherein

A^(2c) is ═N(→O)—;

R^(3c) is a trifluoromethyl group; and

R^(5c) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom: (N-oxide). and

The compound represented by the formula (1-4), wherein

A^(2c) is ═CR^(8c)—;

R⁸ is a C1-C3 alkoxy group, a C1-C3 alkylsulfanyl group, a halogen atom, or a hydrogen atom;

R^(3c) is a trifluoromethyl group; and

R^(5c) is a C1-C3 perfluoroalkyl group, a C1-C3 perfluoroalkoxy group, a C1-C3 perfluoroalkylsulfanyl group, a C1-C3 perfluoroalkylsulfinyl group, a C1-C3 perfluoroalkylsulfonyl group, or a halogen atom; or N-oxide thereof.

Next, a process for preparing the present fused heterocyclic compound is explained.

The present fused heterocyclic compound and intermediate compounds can be prepared, for example, according to the below-mentioned (Process 1) to (Process 24).

(Process 1)

A present fused heterocyclic compound of formula (1) wherein n is 1 or 2 can be prepared by oxidizing a present fused heterocyclic compound of formula (1) wherein n is 0.

[wherein, each symbol is the same as defined in formula (1)]

A present fused heterocyclic compound of formula (1-n1) (when n is 1 in the formula (1)) can be prepared by oxidizing a present fused heterocyclic compound (1-n0) (when n is 0 in the formula (1)) with an oxidizing agent.

The reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aliphatic hydrogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixed solvents thereof.

Examples of the oxidizing agent to be used include sodium periodate and m-chloroperoxybenzoic acid.

In the reaction, the oxidizing agent is used usually within a range of 1 to 3 molar ratio(s) as opposed to 1 mole of the present fused heterocyclic compound (1-n0). Preferably, the oxidizing agent is used within a range of 1 to 1.2 molar ratio(s) as opposed to 1 mole of the present fused heterocyclic compound (1-n0).

The reaction temperature is usually within a range of −20 to 80° C. The reaction period of the reaction is usually within a range of 0.1 to 12 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are, if necessary, worked up (for example, washing with an aqueous solution of a reducing agent (such as sodium sulfite and sodium thiosulfate) and/or an aqueous solution of a base (such as sodium hydrogen carbonate), drying and concentration) to isolate the present fused heterocyclic compound (1-n1). The isolated present fused heterocyclic compound (1-n1) may be further purified, for example, by chromatography and recrystallization.

A present fused heterocyclic compound of formula (1-n2) (when n is 2 in the formula (1)) can be prepared by oxidizing the present fused heterocyclic compound of formula (1-n1) (when n is 1 in the formula (1)).

The reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aliphatic hydrogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acids such as acetic acid; water; and mixed solvents thereof.

Examples of the oxidizing agent to be used include m-chloroperoxybenzoic acid and hydrogen peroxide.

In the reaction, the oxidizing agent is used usually within a range of 1 to 4 molar ratio(s) as opposed to 1 mole of the present fused heterocyclic compound (1-n1). Preferably, the oxidizing agent is used within a range of 1 to 2 molar ratio(s) as opposed to 1 mole of the present fused heterocyclic compound (1-n1).

The reaction temperature is usually within a range of −20 to 120° C. The reaction period of the reaction is usually within a range of 0.1 to 12 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are, if necessary, worked up (for example, washing with an aqueous solution of a reducing agent (such as sodium sulfite and sodium thiosulfate), an aqueous solution of a base (such as sodium hydrogen carbonate), drying and concentration) to isolate the present fused heterocyclic compound (1-n2). The isolated present fused heterocyclic compound (1-n2) may be further purified, for example, by chromatography and recrystallization.

Also, the present fused heterocyclic compound of formula (1-n2) (when n is 2 in the formula (1)) can be prepared by oxidizing the present fused heterocyclic compound (1-n0) (when n is 0 in the formula (1)) with an oxidizing agent in one step (one-pot).

The reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aliphatic hydrogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acids such as acetic acid; water; and mixed solvents thereof.

Examples of the oxidizing agent to be used include m-chloroperoxybenzoic acid and hydrogen peroxide.

The reaction may be also carried out, if necessary, in the presence of a catalyst.

Examples of the catalyst to be used include sodium tungstate.

In the reaction, the oxidizing agent is used usually within a range of 2 to 5 molar ratio(s), and the catalyst is used usually within a range of 0.01 to 0.5 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (1-n0). Preferably, the oxidizing agent is used usually within a range of 2 to 3 molar ratio(s), and the catalyst is used usually within a range of 0.01 to 0.5 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (1-n0).

The reaction temperature is usually within a range of 0 to 120° C. The reaction period of the reaction is usually within a range of 0.1 to 12 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are, if necessary, worked up (for example, washing with an aqueous solution of a reducing agent (such as sodium sulfite and sodium thiosulfate) and/or an aqueous solution of a base (such as sodium hydrogen carbonate), drying and concentration) to isolate the present fused heterocyclic compound (1-n2). The isolated present fused heterocyclic compound (1-n2) may be further purified, for example, by chromatography and recrystallization.

(Process 2)

A present fused heterocyclic compound can be prepared by reacting an intermediate compound (M1) with an intermediate compound (M2) or an intermediate compound (M18) to afford an intermediate compound (M3), followed by performing an intramolecular condensation of the obtained intermediate compound (M3). In this reaction, a production of the intermediate compound (M3) and an intramolecular condensation thereon may be occurred concurrently, resulting in no confirmation of the intermediate compound (M3).

[wherein, each symbol is the same as defined in the formula (1)]

The intermediate compound (M3) may be prepared by reacting the intermediate compound (M) with the intermediate compound (M2) in the presence of a condensation agent.

This reaction is usually carried out in the presence of a solvent. Examples of the solvent to be used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran (hereinafter, sometimes referred to as THF and methyl tert-butyl ether; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; aromatic hydrocarbons such as toluene, benzene and xylene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; aprotic polar solvents such as N,N-dimethylformamide (hereinafter, sometimes referred to as DHF), N-methylpyrrolidone (hereinafter, sometimes referred to as NMP), 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide (hereinafter, sometimes referred to as DMSO); and nitrogen-containing aromatic compounds such as pyridine and quinoline; and mixed solvents thereof.

The condensation agent to be used include 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (hereinafter, sometimes referred to as EDC hydrochloride), 1,3-dicyclohexylcarbodiimide. The reaction may be also carried out, if necessary, in the presence of a catalyst.

Examples of the catalyst to be used include 1-hydroxybenzotriazole (hereinafter, sometimes referred to as HOBt).

In the reaction, the intermediate compound (M2) is used usually within a range of 0.5 to 2 molar ratio(s), the condensation agent is used usually within a range of 1 to 5 molar ratio(s), and the catalyst is used usually within a range of 0.01 to 1 molar ratio(s), as opposed to 1 mole of the intermediate compound (M1).

The reaction temperature is usually within a range of 0 to 120° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are then extracted with organic solvent(s), and the resulting organic layers are concentrated; the reaction mixtures are added into water and the resulting solids are collected by filtration; or the solids formed in the reaction mixtures are collected by filtration, to isolate the intermediate compound (M3). The isolated intermediate compound (M3) may be further purified, for example, by recrystallization and chromatography.

Also, the intermediate compound (M3) may be prepared by reacting the intermediate compound (M1) with the intermediate compound (M18).

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

The reaction may be also carried out, if necessary, in the presence of a base.

Examples of the base to be used include alkali metal carbonates such as sodium carbonate and potassium carbonate; tertiary amines such as triethylamine and N,N-diisopropylethylamine; and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.

In the reaction, the intermediate compound (M18) is used usually within a range of 1 to 3 molar ratio(s), and the base is used usually within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the intermediate compound (M1).

The reaction temperature is usually within a range of −20 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are extracted with organic solvent(s), and the resulting organic layers are, if necessary, worked up (for example, drying and concentration) to isolate the intermediate compound (M3). The intermediate compound (M3) may be further purified, for example, by chromatography and recrystallization.

The present fused heterocyclic compound (1) can be prepared by performing an intramolecular condensation of the intermediate compound (M3).

The reaction is usually carried out in the presence of a solvent. Examples of the solvent to be used in the reaction include ethers such as 1,4-dioxane, diethyl ether, THF and methyl tert-butyl ether; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene; aromatic hydrocarbons such as toluene, benzene and xylene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; aprotic polar solvent such as DMF, NMP, 1,3-dimethyl-2-imidazolidinone and DMSO; nitrogen-containing aromatic compounds such as pyridine and quinoline; and mixed solvents thereof.

In the reaction, if necessary, a condensation agent, an acid, a base or a chlorinating agent may be used.

Examples of the condensation agent to be used include acid anhydrides such as acetic anhydride, trifluoroacetic anhydride; EDC hydrochloride; a mixture of triphenylphosphine, base and carbon tetrachloride or carbon tetrabromide; and a mixture of triphenylphosphine and azodiesters such as diethyl azodicarboxylate.

Examples of the acid to be used include sulfonic acids such as para-toluenesulfonic acid; carboxylic acids such as acetic acid; and polyphosphoric acid.

Examples of the base to be used include pyridine, picoline, 2,6-lutidine and 1,8-diazabicyclo[5.4.0]-7-undecene (hereinafter, sometimes referred to as DBU), nitrogen-containing heterocyclic compounds such as 1,5-diazabicyclo[4.3.0]-5-nonene; tertiary amines such as triethylamine and N,N-diisopropylethylamine; and inorganic bases such as tripotassium phosphate, potassium carbonate and sodium hydride.

Examples of the chlorinating agent to be used include phosphorus oxychloride.

In the reaction, when a condensation agent is used, the condensation agent is used usually within a range of 1 to 5 molar ratio(s), and when an acid is used, the acid is used usually within a range of 0.1 to 5 molar ratio(s), and when a base is used, the base is used usually within a range of 1 to 5 molar ratio(s), and when a chlorinating agent is used, the chlorinating agent is used usually within a range of 1 to 5 molar ratio(s), as opposed to 1 mole of the intermediate compound (M3).

The reaction temperature is usually within a range of 0 to 200° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are then extracted with organic solvent(s), and the resulting organic layers are concentrated; the reaction mixtures are added into water and the resulting solids are collected by filtration; or the solids formed in the reaction mixture are collected by filtration, to afford the present fused heterocyclic compound (1). The isolated the present fused heterocyclic compound (1) may be further purified, for example, by recrystallization and chromatography.

The present fused heterocyclic compound (1) may be prepared in one step (one-pot) by reacting the intermediate compound (M1) with the intermediate compound (M2) in the presence of a condensation agent.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as 1,4-dioxane, diethyl ether, THF, methyl tert-butyl ether; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene; aromatic hydrocarbons such as toluene, benzene, xylene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; aprotic polar solvent such as DMF, NMP, 1,3-dimethyl-2-imidazolidinone and DMSO; nitrogen-containing aromatic compounds such as pyridine and quinoline; and mixed solvents thereof.

Examples of the condensation agent to be used include carbodiimides such as EDC hydrochloride and 1,3-dicyclohexylcarbodiimide.

The reaction may be carried out, if necessary, in the presence of a catalyst.

Examples of the catalyst to be used include 1-hydroxybenzotriazole.

In the reaction, the intermediate compound (M2) is used usually within a range of 0.5 to 2 molar ratio(s), the condensation agent is used usually within a range of 1 to 5 molar ratio(s) and the catalyst is used usually within a range of 0.01 to 1 molar ratio(s), as opposed to 1 mole of the intermediate compound (M1).

The reaction temperature is usually within a range of 0 to 200° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are then extracted with organic solvent(s), and the resulting organic layers are concentrated; the reaction mixtures are added into water and the resulting solids are collected by filtration; or the solids formed in the reaction mixture are collected by filtration, to isolate the present fused heterocyclic compound (1). The isolated present fused heterocyclic compound (1) may be further purified, for example, by recrystallization and chromatography.

Also, the present fused heterocyclic compound (1) can be prepared in one step (one-pot) by reacting the intermediate compound (M1) with the intermediate compound (M18).

The reaction is usually carried out in the presence or absence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

The reaction may be also carried out, if necessary, in the presence of a base.

Examples of the base to be used include alkali metal carbonates such as sodium carbonate and potassium carbonate; tertiary amines such as triethylamine and N,N-diisopropylethylamine; and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.

In the reaction, the intermediate compound (M18) is used usually within a range of 1 to 3 molar ratio(s), and the base is usually within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the intermediate compound (M1).

The reaction temperature is usually within a range of 20 to 200° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are extracted with organic solvent(s), and the resulting organic layers are, if necessary, worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (1). The isolated present fused heterocyclic compound (1) may be further purified, for example, by chromatography and recrystallization.

(Process 3)

A present fused heterocyclic compound of formula (P20) (when A¹ represents a sulfur atom and A² represents a nitrogen atom in the formula (1)) can be prepared by reacting an intermediate compound (M9) with an intermediate compound (M2) or an intermediate compound (M18) to afford an intermediate compound (114), followed by reacting the obtained intermediate compound (M14) with a sulfuring agent.

[wherein, each symbol is the same as defined in the formula (1)]

The intermediate compound (M14) can be prepared by reacting the intermediate compound (M9) with the intermediate compound (M2) in the presence of a condensation agent.

The reaction is carried out usually in the presence or absence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; nitrogen-containing aromatic compounds such as pyridine and quinoline; and mixed solvents thereof.

Examples of the condensation agent to be used include carbodiimides such as EDC hydrochloride and 1,3-dicyclohexylcarbodiimide, and BOP reagent (for example, benzotriazol-1-yloxy-trisdimetylamino phosphonium).

In the reaction, the intermediate compound (M2) is used usually within a range of 1 to 3 molar ratio(s) and the condensation agent is used usually within a range of 1 to 5 molar ratio(s), as opposed to 1 mole of the intermediate compound (M9).

The reaction temperature is usually within a range of 0 to 200° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are extracted with organic solvent(s), and the resulting organic layers are, if necessary, worked up (for example, drying and concentration) to isolate the intermediate compound (M14). The isolated intermediate compound (M14) may be further purified, for example, by chromatography and recrystallization.

Also, the intermediate compound (M14) can be prepared by reacting the intermediate compound (M9) with the intermediate compound (M18).

The reaction is carried out usually in the presence or absence of a solvent. If necessary, the reaction may be also carried out in the presence of a base.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; nitrogen-containing aromatic compounds such as pyridine and quinoline; and mixed solvents thereof.

Examples of the base to be used include alkali metal carbonates such as sodium carbonate and potassium carbonate; tertiary amines such as triethylamine and N,N-diisopropylethylamine; and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. In the reaction, the intermediate compound (M18) is used usually within a range of 1 to 3 molar ratio(s), and the base is used usually within a range of 1 to 5 molar ratio(s), as opposed to 1 mole of the intermediate compound (M9).

The reaction temperature is usually within a range of 0 to 200° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are extracted with organic solvent(s), and the resulting organic layers are, if necessary, worked up (for example, drying and concentration) to isolate the intermediate compound (M14). The isolated intermediate compound (M14) may be further purified, for example, by chromatography and recrystallization.

The present fused heterocyclic compound (P20) can be prepared by reacting the intermediate compound (14) with a sulfurizing agent.

The reaction is carried out in the presence or absence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether and diglyme; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene; aromatic hydrocarbons such as toluene, benzene and xylene; nitriles such as acetonitrile; nitrogen-containing aromatic compounds such as pyridine, picoline, lutidine and quinoline; and mixed solvents thereof.

Examples of the sulfurizing agent to be used include phosphorus pentasulfide and Lawesson's reagent (2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide).

In the reaction, the sulfurizing agent is used usually within a range of 1 to 3 molar ratio(s) as opposed to 1 mole of the intermediate compound (M14).

The reaction temperature is usually within a range of 0 to 200° C. The reaction period of the reaction is usually within a range of 1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are then extracted with organic solvent(s), and the resulting organic layers are concentrated; the reaction mixtures are added into water and the resulting solids are collected by filtration; or the solids formed in the reaction mixture are collected by filtration, to isolate the present fused heterocyclic compound (P20). The isolated present heterocyclic compound (P20) may be further purified, for example, by recrystallization and chromatography.

(Process 4)

A present fused heterocyclic compound can be prepared by reacting an intermediate compound (M1) with an intermediate compound (M4) in the presence of an oxidizing agent.

[wherein, each symbol is the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include alcohols such as methanol and ethanol; ethers such as 1,4-dioxane, diethyl ether, THF and methyl tert-butyl ether; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene; aromatic hydrocarbons such as toluene, benzene and xylene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; aprotic polar solvent such as DM4F, NMP, 1,3-dimethyl-2-imidazolidinone and DMSO; nitrogen-containing aromatic compounds such as pyridine and quinoline; and mixed solvents thereof.

The reaction may be also carried out, for necessary, in the presence of an acid.

Examples of the acid to be used in the reaction include sulfonic acids such as paratoluenesulfonic acid; carboxylic acids such as acetic acid; and polyphosphoric acid.

The reaction may be also carried out, if necessary, in the presence of a sulfite.

Examples of the sulfite to be used in the reaction include sulfites such as sodium hydrogen sulfite and sodium bisulfite.

Examples of the oxidizing agent to be used include oxygen (for example, molecular oxygen), copper chloride(II) and DDQ.

In the reaction, the intermediate compound (M4) is used usually within a range of 1 to 2 molar ratio(s), the acid is used usually within a range of 0.1 to 2 molar ratio(s), the sulfites is used usually within a range of 1 to 5 molar ratio(s), and the oxidizing agent is used usually within a range of 1 to 5 molar ratio(s), as opposed to one mole of the intermediate compound (M1).

The reaction temperature is usually within a range of 0 to 200° C. The reaction period of the reaction is usually within a range of 1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are then extracted with organic solvent(s), and the resulting organic layers are concentrated; the reaction mixtures are added into water and the resulting solids are collected by filtration; or the solids formed in the reaction mixture are collected by filtration, to isolate the present fused heterocyclic compound (1). The isolated present heterocyclic compound (1) may be further purified, for example, by recrystallization and chromatography.

(Process 5)

A present fused heterocyclic compound (1) (when n is 0 in the formula (1)) can be prepared by reacting an intermediate compound (M6) with a compound (M7) in the presence of a base.

[wherein, V² represents a halogen atom, and the other symbols are the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; water; and mixed solvents thereof.

Examples of the base to be used include alkali metal carbonates such as sodium carbonate and potassium carbonate; and alkali metal hydrides such as sodium hydride.

In the reaction, the compound (M7) is used usually within a range of 1 to 10 molar ratio(s), and the base is used usually within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the intermediate compound (M6).

The reaction temperature is usually within a range of 0 to 150° C. The reaction period of the reaction is usually within a range of 0.5 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (1) (when n is 0 in the formula (1)). The isolated present fused heterocyclic compound (1) (when n is 0 in the formula (1)) may be further purified, for example, by chromatography and recrystallization.

In the reaction, V² is preferably a fluorine atom and a chlorine atom.

(Process 6)

An intermediate compound (M6) can be prepared by reacting an intermediate compound (M1) with an intermediate compound (M19) or an intermediate compound (M39) to afford an intermediate compound (M20), followed by performing an intramolecular condensation of the obtained intermediate compound (M20). In this reaction, a production of the intermediate compound (M20) and an intramolecular condensation thereon may be occurred concurrently, resulting in no confirmation of the intermediate compound (M20).

[wherein, V² represents a halogen atom, and the other each symbol is the same as defined in the formula (1)]

The intermediate compound (M20) can be prepared by using the intermediate compound (M19) instead of the intermediate compound (M2) according to Process 2.

The intermediate compound (M20) can be prepared by using the intermediate compound (M39) instead of the intermediate compound (M18) according to Process 2.

The intermediate compound (M6) can be prepared by using the intermediate compound (M20) instead of the intermediate compound (M3) according to Process 2.

Also, the intermediate compound (M6) can be prepared by using the intermediate compound (M19) instead of the intermediate compound (M2) according to Process 2 in one step (one-pot).

Also, the intermediate compound (M6) can be also prepared by using the intermediate compound (M39) instead of the intermediate compound (M2) according to Process 2 in one step (one-pot).

In the reaction, V² represents preferably a fluorine atom or a chlorine atom.

(Process 7)

An intermediate compound (M3) (when n is 0 in the formula (M3)) can be prepared by reacting an intermediate compound (M20) with a compound (M7). Also, the obtained intermediate compound (M3) can be performed on intramolecular condensation to afford a present fused heterocyclic compound (1) (when n is 0 in the formula (1)).

[wherein, V² represents a halogen atom, and the other each symbol is the same as defined in the formula (1)]

The intermediate compound (M3) (when n is 0 in the formula (M3)) can be prepared by using the intermediate compound (M20) instead of the intermediate compound of formula (M6) according to Process 5.

The present fused heterocyclic compound (1) (when n is 0 in the formula (1)) can be prepared by using the intermediate compound (M3) (when n is 0 in the formula (M3)) instead of the intermediate compound (M3) according to Process 2.

Also, the present fused heterocyclic compound (1) (when n is 0 in the formula (1)) can be also prepared by using the intermediate compound (M20) instead of the intermediate compound (M6) according to Process 5 in one step (one-pot).

In the reaction, V² represents preferably a fluorine atom or a chlorine atom.

(Process 8)

A present fused heterocyclic compound (1) (when n is 0 in the formula (1)) can be prepared by reacting an intermediate compound (M8) or a disulfide compound thereof, that is, an intermediate compound (M8′) with a compound (M17) in the presence of a base.

[wherein, L represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group or a methanesulfonyloxy group, and the other each symbol is the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the base to be used include an alkali metal or alkaline-earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride; inorganic bases such as sodium carbonate and potassium carbonate; and organic bases such as triethylamine.

When the intermediate compound (M8′) being the disulfide compound is used, the reaction is usually carried out in the presence of a reducing agent.

Examples of the reducing agent to be used in the reaction include hydroxymethanesulfinic acid sodium salt (Trade name: Rongalite).

In the reaction, the compound (M17) is used usually within a range of 1 to 10 molar ratio(s), and the base is used usually within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the intermediate compound (M8). Also, when the intermediate compound (M8′) being the disulfide compound is used, the compound (M17) is used usually within a range of 2 to 10 molar ratio(s), the base is used usually within a range of 2 to 10 molar ratio(s), and the reducing agent is used usually within a range of 1 to 5 molar ratio(s), as opposed to 1 mole of the intermediate compound (M8′).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (1) (when n is 0 in the formula (1)). The isolated present fused heterocyclic compound (1) (when n is 0 in the formula (1)) may be further purified, for example, by chromatography and recrystallization.

(Process 9)

A present fused heterocyclic compound (1) (when n is 0 in the formula (1)) can be prepared by reacting an intermediate compound (M8′) with a compound (M17′-1) or a compound (M17′-2).

[wherein, V³ represents a chlorine atom, a bromine atom or an iodine atom; and the other each symbol is the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

In the reaction, the compound (M17′-1) is used usually within a range of 1 to 2 molar ratio(s) as opposed to 1 mole of the intermediate compound (M8′). Also, when the compound (M17′-2) is used, the compound (M17′-2) is used usually within a range of 1 to 2 molar ratio(s) as opposed to 1 mole of the intermediate compound (M8′).

The reaction temperature is usually within a range of −80 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (1) (when n is 0 in the formula (1)). The isolated present fused heterocyclic compound (1) (when n is 0 in the formula (1)) may be further purified, for example, by chromatography and recrystallization.

(Process 10)

An intermediate compound (M8) can be prepared by reacting an intermediate compound (M6) with a sulfurizing agent. Also, an intermediate compound (M8′) being a disulfide compound can be prepared by oxidizing an intermediate compound (M8).

[wherein, V² represents a halogen atom, and the other each symbol is the same as defined in the formula (1)]

The intermediate compound (M8) can be prepared by using sulfides such as sodium sulfide, sodium hydrogen sulfide or hydrogen sulfide instead of the compound (M7) according to Process 5.

In this reaction, the conversion reaction of the intermediate compound (M8) to the intermediate compound (M8′) can easily proceed and the intermediate compound (M8′) is sometimes formed during a synthesis of the intermediate compound (MB). In the reaction, V² is preferably a fluorine atom or a chlorine atom.

The intermediate compound (M8′) can be prepared by reacting two molecules of the intermediate compound (M8) in the presence of an oxidizing agent.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include water; alcohols such as methanol and ethanol; ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; carboxylic acids such as acetic acid; and mixed solvents thereof. Examples of the oxidizing agent to be used include oxygen (such as molecular oxygen), iodine, hydrogen peroxide and potassium ferricyanide.

In the reaction, the oxidizing compound (M8) is used usually within a range of 0.5 to 10 molar ratio(s) as opposed to 1 mole of the intermediate compound (M8).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M8′). The obtained intermediate compound (M8′) may be further purified, for example, by chromatography and recrystallization.

(Process 11)

A present fused heterocyclic compound (P3) (when A¹ represents —NR^(7′)— in the formula (1)) can be prepared by reacting a present fused heterocyclic compound (P2) (when A1 represents —NH— in the formula (1)) with a compound (M10) in the presence of a base.

[wherein, R^(7′) represents any group as R⁷ defined in the formula (1) other than a hydrogen atom, L represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group and a methanesulfonyloxy group; and the other each symbol is the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the base to be used include alkali metal or alkaline-earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride; inorganic bases such as sodium carbonate and potassium carbonate; and organic bases such as triethylamine.

In the reaction, the compound (M10) is usually used within a range of 1 to 5 molar ratio(s), and the base is used usually within a range of 1 to 3 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P2).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P3). The obtained present fused heterocyclic compound (P3) may be further purified, for example, by chromatography and recrystallization.

(Process 12)

An intermediate compound (M2) can be prepared by hydrolyzing an intermediate compound (M37).

[wherein, each symbol is the same as defined in the formula (1)]

In the case of a hydrolysis with an acid, the reaction is usually carried out by using an aqueous solution of an acid as solvent.

Examples of the acid to be used include mineral acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid; and organic acids including, for example, organic carboxylic acids such as acetic acid and trifluorocarboxylic acid.

In the reaction, an acid is used usually within a range of 1 to 10 molar ratio(s) as opposed to 1 mole of the intermediate compound (M37).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate intermediate compound (M2). The obtained intermediate compound (M2) may be further purified, for example, by chromatography and recrystallization.

In the case of a hydrolysis with a base, the reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; alcohols such as methanol and ethanol; water; and mixed solvents thereof.

Examples of the base to be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

In the reaction, a base is used usually within a range of 1 to 10 molar ratio(s) as opposed to one mole of the intermediate compound (M37).

The reaction temperature is usually within a range of 0 to 120° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction solutions are acidified and the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M2). The isolated intermediate compound (M2) may be further purified, for example, by chromatography and recrystallization.

(Process 13)

An intermediate compound (M18) can be prepared by reacting an intermediate compound (M2) with a chlorinating agent.

[wherein, each symbol is the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tent-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrogenated hydrocarbons such as dichloromethane and chloroform; and mixed solvents thereof.

Examples of the chlorinating agent to be used include sulfonyl chloride, oxalyl dichloride and phosphorus oxychloride.

In the reaction, the chlorinating agent is used usually within a range of 1 to 5 molar ratio(s) as opposed to one mole of the intermediate compound (M2).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reation solvents are distilled off to isolate the intermediate compound (M18).

(Process 14)

An intermediate compound (M2), an intermediate compound (M4) or an intermediate compound (M37) can be prepared by reacting an intermediate compound (M19), an interdicted compound (M22) or an intermediate compound (M36) with a compound (MT), if necessary, followed by oxidizing each the obtained intermediate compound.

[wherein, V² represents a halogen atom, and the other each symbol is the same as defined in the formula (1)]

The intermediate compound (M2) (when n is 0) can be prepared by using the intermediate compound (M19) instead of the intermediate compound (M6) according to Process 5.

The intermediate compound (M4) (when n is 0) can be prepared by using the intermediate compound (M22) instead of the intermediate compound (M6) according to Process 5.

The intermediate compound (M37) (when n is 0) can be prepared by using the intermediate compound (M36) instead of the intermediate compound (M6) according to Process 5.

The intermediate compound (M2) (when n is 1 or 2) can be prepared by using the intermediate compound (M2) (when n is 0) instead of the present fused heterocyclic compound (1) (when n is 0) according to Process 1.

The intermediate compound (M4) (when n is 1 or 2) can be prepared by using the intermediate compound (M4) (when n is 0) instead of the present fused heterocyclic compound (1) (when n is 0) according to Process 1.

The intermediate compound (M37) (when n is 1 or 2) can be prepared by using the intermediate compound (M37) (when n is 0) instead of the present fused heterocyclic compound (1) (when n is 0) according to Process 1.

In the reaction, V² represents preferably a fluorine atom or a chlorine atom.

(Process 15)

An intermediate compound (M30) can be prepared by performing a nitration reaction of an intermediate compound (M29) or by reacting an intermediate compound (M33) with a compound (M28). The obtained intermediate compound (M30) can be reduced to afford an intermediate compound (M1) (when A¹ represents —NR⁷— in the formula (M1)).

[wherein, each symbol is the same as defined in the formula (1)]

The intermediate compound (M30) can be prepared by reacting the intermediate compound (M33) with the compound (M28) in the presence of a base.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

The reaction may be carried out, if necessary, in the presence of a base. Examples of the base to be used include alkali metal hydrides such as sodium hydride; alkali metal carbonates such as sodium carbonate and potassium carbonate; tertiary amines such as triethylamine and N,N-diisopropylethylamine; and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.

In the reaction, the compound (M28) is used usually within a range of 1 to 10 molar ratio(s), and the base is used usually within a range of 0 to 10 molar ratio(s), as opposed to 1 mole of the intermediate compound (M33).

The reaction temperature is usually within a range of 0 to 150° C. The reaction period of the reaction is usually within a range of 0.5 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M30). The isolated intermediate compound (M30) may be further purified, for example, by chromatography and recrystallization.

The intermediate compound (M30) can be prepared by reacting the intermediate compound (M29) with a nitrating agent.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aliphatic hydrogenated hydrocarbons such as dichloromethane and chloroform; acids such as acetic acid, concentrated sulfuric acid and concentrated nitric acid; water; and mixed solvents thereof.

The nitrating agent to be used in the reaction includes a concentrated nitric acid.

In the reaction, the nitrating agent is used usually within a range of 1 to 3 molar ratio(s) as opposed to 1 mole of the intermediate compound (M29).

The reaction temperature is usually within a range of −10 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M30). The isolated intermediate compound (M30) may be further purified, for example, by chromatography and recrystallization.

Also, in the case where in the formula (M30), R⁷ represents a hydrogen atom, the compounds of formula (M30) wherein R⁷ represents any group other than a hydrogen atom can be prepared by using the intermediate compound (M30) wherein R⁷ represents a hydrogen atom instead of the compound (P2) according to Process 11.

The intermediate compound (M1) (when A¹ represents —NR⁷—) can be prepared by reacting the intermediate compound (M30) with hydrogen gas in the presence of a catalyst for hydrogenation.

The reaction is carried out under hydrogen atmosphere of usually 1 to 100 atmospheric pressure(s) and usually in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; alcohols such as methanol and ethanol; water; and mixed solvents thereof.

The catalysts for hydrogenation to be used in the reaction include transition metal compounds such as palladium-carbon, palladium hydroxide, raney nickel and platinum oxide.

In the reaction, the hydrogen gas is used usually within a range of 3 molar ratios, and the catalysts for hydrogenation are used usually within a range of 0.001 to 0.5 molar ratio(s), as opposed to 1 mole of the intermediate compound (M30).

The reaction may be carried out, if necessary, in the presence of an acid or a base and the others.

Examples of the acids to be used in the reaction include acids such as acetic acid and hydrochloric acid, and examples of the base to be used include tertiary amines such as triethylamine and magnesium oxide.

The reaction temperature is usually within a range of −20 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are filtered and, if necessary, are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M1) (when A¹ represents —NR⁷—). The isolated intermediate compound (M1) (when A¹ represents —NR⁷—) may be further purified, for example, by chromatography and recrystallization.

Also, the intermediate compound (M30) can be prepared as mentioned below, for example, by acetylating the intermediate compound (M29′) to afford the intermediate compound (M29′), followed by performing a nitration reaction of the obtained intermediate compound (M29′) to afford the intermediate compound (M30′) and further by hydrolyzing the obtained intermediate compound (M30′).

[wherein, each symbol is the same as defined in the formula (1)]

The intermediate compound (M29′) can be prepared by reacting the intermediate compound (M29) with an acylating agent.

The reaction is carried out usually in the presence of a solvent or by using the acylating agent as solvent.

Examples of the solvent to be used in the reaction include aliphatic hydrogenated hydrocarbons such as dichloromethane and chloroform; aliphatic hydrogenated hydrocarbons such as dichloromethane and chloroform; ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof. Examples of the acylating agent to be used in the reaction include acetic anhydride and para-acetoxy nitrobenzene.

The reaction may be also carried out, if necessary, in the presence of a base. Examples of the base to be used include tertiary amines such as triethylamine and N,N-diisopropylethylamine; and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.

In the reaction, the acylating agent is used within a range of 1 or more molar ratio(s), and the base is used usually within a range of 0.1 to 10 molar ratio(s), as opposed to 1 mole of the intermediate compound (M29).

The reaction temperature is usually within a range of 0 to 150° C. The reaction period of the reaction is usually within a range of 0.5 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M29′). The isolated intermediate compound (M29′) may be further purified, for example, by chromatography and recrystallization.

The intermediate compound (M30′) can be prepared by using the intermediate compound (M29′) instead of the intermediate compound (M29) according to Process 15.

The intermediate compound (M30) can be prepared by hydrolyzing the intermediate compound (M30′) in the presence of an acid or a base.

In the case of a hydrolysis with an acid, the reaction is usually carried out by using an aqueous solution of the acid as solvent.

Examples of the acid to be used in the reaction include mineral acids such as hydrochloric acid and sulfuric acid; and organic acid including, for example, organic carboxylic acids such as acetic acid and trifluoroacetic acid.

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M30). The isolated intermediate compound (M30) may be further purified, for example, by chromatography and recrystallization.

In the case of a hydrolysis with a base, the reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; alcohols such as methanol and ethanol; water; and mixed solvents thereof.

Examples of the base to be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and hydrazine.

In the reaction, the base is used usually within a range of 1 to 10 molar ratio(s) as opposed to 1 mole of the intermediate compound (M30′).

The reaction temperature is usually within a range of 0 to 120° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction solutions are acidified, and the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M30). The isolated intermediate compound (M30) may be further purified, for example, by chromatography and recrystallization.

(Process 16)

An intermediate compound (M1) (when A¹ represents —NR⁷—) can be prepared by brominating an intermediate compound (M29) to afford an intermediate compound (M35), followed by aminating the obtained intermediate compound (M35).

[wherein, each symbol is the same as defined in the formula (1)]

The intermediate compound (M35) can be prepared by reacting the intermediate compound (M29) with a brominating agent.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include water; acetic acid; ethers such as 1,4-dioxane, diethyl ether and THF; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the brominating agent to be used include N-bromosuccinimide and bromine.

The brominating agent is used usually within a range of 1 to 3 molar ratio(s) as opposed to 1 mole of the intermediate compound (M29).

The reaction temperature is usually within a range of −10 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are added into water and are then extracted with organic solvent(s), and the resulting organic layers are concentrated; the reaction mixtures are added into water and the resulting solids are collected by filtration; or the solids formed in the reaction mixture are collected by filtration, to afford the intermediate compound (M35). The isolated intermediate compound (M35) may be further purified, for example, by recrystallization and chromatography.

The intermediate compound (M1) (when A¹ represents —NR⁷—) can be prepared by reacting the intermediate compound (M35) with an aminating agent in the presence of a copper compound.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include water; alcohols such as methanol and ethanol; ethers such as 1,4-dioxane, diethyl ether and THF; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; nitrogen-containing aromatic compounds such as pyridine and quinoline; and mixed solvents thereof.

The aminating agent to be used in the reaction includes ammonia, aqueous ammonia and lithium amide.

The copper compound to be used in the reaction includes copper, copper iodide(I), copper oxide(I), copper oxide(II), acetylacetone copper(II, copper acetate(II) and copper sulfate(II).

The reaction may be also carried out, if necessary, in the presence of a ligand.

Examples of the ligand to be used in the reaction include acetylacetone, salen (N,N′-bis(salicylidene)ethylenediamine) and phenanthroline.

The reaction may be also carried out, if necessary, in the presence of a base.

Examples of the base to be used include nitrogen-containing heterocyclic compounds such as pyridine, picoline, 2,6-lutidine, DBU, 1,5-diazabicyclo[4.3.0]-5-nonene; tertiary amines such as triethylamine and N,N-diisopropylethylamine; and inorganic bases such as tripotassium phosphate, potassium carbonate, cesium carbonate and sodium hydroxide.

The aminating agent is used usually within a range of 1 to 5 molar ratio(s), the copper compound is used usually within a range of 0.02 to 0.5 molar ratio(s), the ligand is used usually within a range of 0.02 to 2 molar ratio(s) and the base is used usually within a range of 1 to 5 molar ratio(s), as opposed to 1 mole of the intermediate compound (M35).

The reaction temperature is usually within a range of 30 to 200° C. The reaction period of the reaction is usually within a range of 0.1 to 48 hours.

When the reaction is completed, the reaction mixtures are added into water and are then extracted with organic solvent(s), and the resulting organic layers are concentrated; the reaction mixtures are added into water and the resulting solids are collected by filtration; or the solids formed in the reaction mixture are collected by filtration, to afford the intermediate compound (M1) (when A¹ represents —NR⁷—). The isolated intermediate compound (M1) (when A¹ represents —NR⁷—) may be further purified, for example, by recrystallization and chromatography.

(Process 17)

An intermediate compound (M1) (when A¹ represents an oxygen atom) can be prepared by performing a nitration reaction of an intermediate compound (M31) to afford an intermediate compound (M32), followed by reducing the obtained intermediate compound (M32).

[wherein, each symbol is the same as defined in the formula (1)]

The intermediate compound (M32) can be prepared by using the intermediate compound (M31) instead of the intermediate compound (M29) according to Process 15.

The intermediate compound (M1) (when A¹ represents an oxygen atom) can be prepared by using the intermediate compound (M32) instead of the intermediate compound (M30) according to Process 15.

(Process 18)

An intermediate compound (M1) can be prepared by reacting an intermediate compound (M33) with a sulfurizing agent to afford an intermediate compound (M34), followed by reacting the obtained intermediate compound (M34) with a reducing agent.

[wherein, each symbol is the same as defined in the formula (1)]

The intermediate compound (M34) can be prepared by reacting the intermediate compound (M33) with a thiourea in the presence of a base.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include alcohols such as methanol and ethanol; water; and mixed solvents thereof.

Examples of the base to be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

In the reaction, the thiourea is used usually within a range of 0.5 to 3 molar ratio(s), and the base is used usually within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the intermediate compound (M33).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, to the reaction mixtures are added an acid, and the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M34). The isolated intermediate compound (M34) may be further purified, for example, by chromatography and recrystallization.

The intermediate compound (M1) (when A¹ represents a sulfur atom) can be prepared by reacting the intermediate compound (M34) with a reducing agent.

The reduction reaction may be carried out, for example, in the presence of metal powder such as zinc powder; acids such as hydrochloric acid and acetic acid; and water.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; eaters such as ethyl acetate and butyl acetate; alcohols such as methanol and ethanol; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the reducing agent to be used in the reaction include metal powder such as iron powder, zinc powder and tin dichloride.

In the reaction, the metal powder is used usually within a range of 3 to 10 molar ratio(s) as opposed to 1 mole of the intermediate compound (M34).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, to the reaction mixtures are added an acid, and the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (M1) wherein A¹ represents a sulfur atom. The isolated intermediate compound (M1) wherein A¹ represents a sulfur atom may be further purified, for example, by chromatography and recrystallization.

(Process 19)

A compound of formula (1) wherein R⁵ represents a C1-C6 perfluoroalkyl group, that is, a present fused heterocyclic compound (P7) can be prepared by reacting a compound of formula (1) wherein R⁵ represents a halogen atom, that is, a present fused heterocyclic compound (P4) with a compound (N11) or a compound (M11′) in the presence of a copper compound.

[wherein, V¹ represents a halogen atom, Rf represents a C1-C6 perfluoroalkyl group, and the other each symbol is the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aromatic hydrocarbons such as toluene and xylene; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof. Examples of the copper compound to be used in the reaction include copper and copper iodide(I). When the compound (M11) is used in the reaction, the compound (M11) is used usually within a range of 1 to 10 molar ratio(s), the copper compound is used usually within a range of 0.5 to 10 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P4).

The reaction temperature is usually within a range of 100 to 200° C. The reaction period of the reaction is usually within a range of 0.5 to 48 hours.

In the reaction, when the intermediate compound (M11′) is used, a potassium fluoride may be optionally added. The compound (M11′) is used usually within a range of 1 to 10 molar ratio(s), the copper compound is used usually within a range of 0.1 to 10 molar ratio(s), and the potassium fluoride is used usually within a range of 0.1 to 5 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P4).

The reaction temperature is usually within a range of 0 to 150° C. The reaction period of the reaction is usually within a range of 0.5 to 48 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P7). The isolated present fused heterocyclic compound (P7) may be further purified, for example, by chromatography and recrystallization. In the reaction, Vi represents preferably a bromine atom and an iodine atom.

(Process 20)

A present fused heterocyclic compound (P9) (when R⁵ represents a —SH group in the formula (1)) can be prepared by reacting a present fused heterocyclic compound (P4) with a sulfurizing agent. Also, the present fused heterocyclic compound (P9) can be oxidized to afford a disulfide compound thereof, that is, an intermediate compound (P9′).

[wherein, V¹ represents a halogen atom, and each other symbols are the same as defined in formula (1)]

The present fused heterocyclic compound (P9) can be prepared by reacting the present fused heterocyclic compound (P4) with a thiolating agent in the presence of a catalyst.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aromatic hydrocarbons such as toluene and xylene; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the thiolating agent to be used in the reaction include sodium sulfide, sodium sulfide nine hydrates and thiourea.

Examples of the catalyst to be used include copper chloride(I), copper bromide(I) and copper iodide(I).

The reaction may be also carried out, if necessary, in the presence of a ligand.

Examples of the ligand to be used in the reaction include acetylacetone, salen and phenanthroline.

The reaction may be also carried out, if necessary, in the presence of a base.

Examples of the base to be used include inorganic bases such as potassium carbonate, cesium carbonate and tripotassium phosphate; and organic bases such as triethylamine.

In the reaction, the thiolating agent is used usually within a range of 1 to 10 molar ratio(s), the catalyst is used usually within a range of 0.1 to 5 molar ratio(s), the ligand is used usually within a range of 0.1 to 5 molar ratio(s), and the base is used usually within a range of 1 to 2 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P4).

The reaction temperature is usually within a range of 50 to 200° C. The reaction period of the reaction is usually within a range of 0.5 to 24 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P9). The isolated present fused heterocyclic compound (P9) may be further purified, for example, by chromatography and recrystallization. In the reaction, V¹ represents preferably a bromine atom and an iodine atom.

In this reaction, the conversion reaction of the intermediate compound (P9) to the intermediate compound (P9′) can easily proceed and the intermediate compound (P9′) is sometimes formed during a synthesis of the intermediate compound (P9).

The intermediate compound (P9′) can be prepared by reacting the present fused heterocyclic compound (P9) with an oxidizing agent.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include water; alcohols such as methanol and ethanol; ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; carboxylic acids such as acetic acid; and mixed solvents thereof.

Examples of the oxidizing agent to be used include oxygen (for example, molecular oxygen), iodine, hydrogen peroxide and potassium ferricyanide.

In the reaction, the oxidizing agent is used usually within a range of 0.5 to 10 molar ratio(s) as opposed to 1 mole of the present fused heterocyclic compound (P9).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (P9′). The isolated intermediate compound (P9′) may be further purified, for example, by chromatography and recrystallization.

Also, the present fused heterocyclic compound (P9) can be prepared by thioesterifying the present fused heterocyclic compound (P4) to afford the intermediate compound (P9-1), followed by hydrolyzing the obtained intermediate compound (P9-1).

[wherein, P^(10′) represents any group as R¹⁰ defined in the formula (1) other than a hydrogen atom, and each other symbol is the same as defined in the formula (1)]

The intermediate compound (P9-1) can be prepared by reacting the present fused heterocyclic compound (P4) with a thioesterifying agent in the presence of a base and a catalyst.

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aromatic hydrocarbons such as toluene and xylene; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the thioesterifying agent include thiobenzoic acid.

Examples of the catalyst to be used include copper chloride(I), copper bromide(I) and copper iodide(I).

The reaction may be carried out, for example, in the presence of a ligand.

Examples of the ligand to be used in the reaction include acetyl acetone, salen and phenanthroline.

Examples of the base to be used include inorganic bases such as potassium carbonate, cesium carbonate, tripotassium phosphate; and organic bases such as triethylamine.

In the reaction, the thioesterifying agent is used usually within a range of 1 to 10 molar ratio(s), the catalyst is used usually within a range of 0.1 to 5 molar ratio(s), the ligand is used usually within a range of 0.1 to 5 molar ratio(s), and the base is used usually within a range of 1 to 2 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P4).

The reaction temperature is usually within a range of 50 to 200° C. The reaction period of the reaction is usually within a range of 0.5 to 24 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (P9-1). The isolated intermediate compound (P9-1) may be further purified, for example, by chromatography and recrystallization.

In the reaction, V¹ represents preferably a bromine atom and an iodine atom.

The present fused heterocyclic compound (P9) can be prepared by hydrolyzing the intermediate compound (P9-1).

In the case of a hydrolysis with an acid, the reaction is usually carried out by using an aqueous solution of the acid as solvent.

Examples of the acid to be used in the reaction include mineral acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid; and organic acid including, for example, organic carboxylic acids such as acetic acid and trifluoroacetic acid.

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P9). The present fused heterocyclic compound (P9) may be further purified, for example, by chromatography and recrystallization.

In the case of a hydrolysis with a base, the reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; alcohols such as methanol and ethanol; water; and mixed solvents thereof.

Examples of the base to be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

In the reaction, the base is used usually within a range of 1 to 10 molar ratio(s) as opposed to 1 mole of the intermediate compound (P9-1).

The reaction temperature is usually within a range of 0 to 120° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction solutions were acidified, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P9). The present fused heterocyclic compound (P9) may be further purified, for example, by chromatography and recrystallization.

In this reaction, the conversion reaction of the present fused heterocyclic compound (P9) to the intermediate compound (P9′) can easily proceed and the intermediate compound (P9′) is sometimes formed during a synthesis of the present fused heterocyclic compound (P9).

(Process 21)

A present fused heterocyclic compound (P10-m0) (when R⁵ represents a —S(O)_(m)R¹⁰ group and also m is 0) can be prepared by reacting a present fused heterocyclic compound (P9) or a disulfide compound thereof, that is, an intermediate compound (P9′) with a compound (M13).

The present fused heterocyclic compound (P10-m0) (when m is 0) can be oxidized to afford the present fused heterocyclic compound (P10) (when R⁵ represents a —S(O)_(m)R¹⁰ group and also m is 1 or 2).

[wherein, R^(10′) represents any group of R¹⁰ defined in formula (1) other than a hydrogen atom, L represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group and a methanesulfonyloxy group, and each other symbol is the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the base to be used include an alkali metal or alkaline-earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride; and inorganic bases such as sodium carbonate, potassium carbonate; and organic bases such as triethylamine.

In the case where the intermediate compound (P9′) being disulfide compound is used, the reaction is usually carried out in the presence of a reducing agent.

Examples of the reducing agent to be used in the reaction include hydroxymethanesulfinic acid sodium salt (Trade name: Rongalite).

In the reaction, the compound (M13) is usually used within a range of 1 to 10 molar ratio(s), and the base is usually used within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P9).

Also, in the case where the intermediate compound (P9′) being disulfide compound is used, the compound (M13) is used usually within a range of 2 to 10 molar ratio(s), the base is used usually within a range of 2 to 10 molar ratio(s), and the reducing agent is used usually within a range of 1 to 5 molar ratio(s), as opposed to 1 mole of the intermediate compound (P9′).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P10-m0) (m is 0). The isolated present fused heterocyclic compound (P10-m0) (m is 0) may be further purified, for example, by chromatography and recrystallization.

Also, among the present fused heterocyclic compound (P10-m0) (when m is 0), the intermediate compound (P9′) (when R^(10′) represents a C1-C6 perfluoroalkyl group) can be prepared by reacting the intermediate compound (P9′), a perfluoroalkyl iodide and a reducing agent. This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the reducing agent to be used in the reaction include tetrakis(dimethylamino)ethylene.

Examples of the perfluoroalkyl iodide include trifluoroiodomethane, iodopentafluoroethane and heptafluoro-2-iodopropane.

In the reaction, the perfluoroalkyl iodide is used usually within a range of 2 to 10 molar ratio(s), and the reducing agent is used usually within a range of 1 to 5 molar ratio(s), as opposed to 1 mole of the intermediate compound (P9′).

The reaction temperature is usually within a range of −80 to 50° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P10-m0) (when m is 0). The isolated present fused heterocyclic compound (P10-m0) (when m is 0) may be further purified, for example, by chromatography and recrystallization.

Among the present fused heterocyclic compound (P10), the present fused heterocyclic compound wherein m is 1 or 2 can be prepared by reacting the present fused heterocyclic compound (P10-m0) (when m is 0) with an oxidizing agent.

This reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include aliphatic hydrogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; carboxylic acids such as acetic acid; water; and mixed solvents thereof.

Examples of the oxidizing agent to be used include m-chloroperoxybenzoic acid or hydrogen peroxide.

The reaction may be also carried out, if necessary, in the presence of a catalyst.

Examples of the catalyst to be used include sodium tungstate.

In the reaction, the oxidizing agent is used usually within a range of 1 to 5 molar ratio(s), and the catalyst is used usually within a range of 0.01 to 0.5 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P10-m0) (when m is 0).

In the preparation of the compound wherein m is 1, the oxidizing agent is used usually within a range of 0.8 to 1.2 molar ratio(s), and the catalyst is used usually within a range of 0.05 to 0.2 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P10-m0) when (m is 0). In the preparation of the compound wherein m is 2, the oxidizing agent is used usually within a range of 1.8 to 5 molar ratio(s), and the catalyst is used usually within a range of 0.05 to 0.2 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P10-m0) (when m is 0).

The reaction temperature is usually within a range of −20 to 120° C. The reaction period of the reaction is usually within a range of 0.1 to 12 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and if necessary, the resulting organic layers are worked up (for example, washing with an aqueous solution of the reducing agent (for example, sodium sulfite, sodium thiosulfate) and/or an aqueous solution of the base (for example, sodium hydrogen carbonate), drying and concentration) to isolate the present fused heterocyclic compound (P10) (when m is 1 or 2). The isolated present fused heterocyclic compound (P10) (when m is 1 or 2) may be further purified, for example, by chromatography and recrystallization.

(Process 22)

A present fused heterocyclic compound (P11) (when R⁵ represents —OH) can be prepared via an intermediate compound (P11′) from the present fused heterocyclic compound (P4).

[wherein, V¹ represents a halogen atom and each other symbol is the same as defined in the formula (1)]

The intermediate compound (P11′) can be prepared by reacting the present fused heterocyclic compound (P4) with benzyl alcohol in the presence of a base.

The reaction is usually carried out in the presence of a solvent or by using benzyl alcohol as solvent.

Examples of the solvent to be used in the reaction include aromatic hydrocarbons such as toluene and xylene; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof. The reaction may be carried out, if necessary, in the presence of a catalyst. Examples of the catalyst to be used include copper halides such as copper chloride(I), copper bromide(I) and copper iodide(I).

The reaction may be also carried out, if necessary, in the presence of a ligand.

Examples of the ligand to be used in the reaction include acetyl acetone, salen and phenanthroline.

The reaction is usually carried out in the presence of a base.

Examples of the base to be used include inorganic bases such as potassium carbonate, cesium carbonate and tripotassium phosphate.

In the reaction, the benzyl alcohol is used usually within a range of 1 to 10 molar ratio(s), the catalyst is used usually within a range of 0.1 to 5 molar ratio(s), the ligand is used usually within a range of 0.1 to 5 molar ratio(s), and the base is used usually within a range of 1 to 2 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P4).

The reaction temperature is usually within a range of 50 to 200° C. The reaction period of the reaction is usually within a range of 0.5 to 24 hours.

When the reaction is completed, the resulting mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the intermediate compound (P11′). The isolated intermediate compound (P11′) may be further purified, for example, by chromatography and recrystallization.

In the reaction, V¹ represents preferably a bromine atom and an iodine atom.

The present fused heterocyclic compound (P11) can be prepared by reacting the intermediate compound (P11′) with hydrogen gas in the presence of a catalyst for hydrogenation.

The reaction is carried out under hydrogen atmosphere of usually 1 to 100 atmospheric pressure(s) and usually in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; alcohols such as methanol and ethanol; water; and mixed solvents thereof.

Examples of the catalyst for hydrogenation to be used in the reaction include transition metal compounds such as palladium-carbon, palladium hydroxide, raney nickel and platinum oxide.

In the reaction, the hydrogen gas is used usually within a range of 3 molar ratios, the catalysts for hydrogenation is used usually within a range of 0.001 to 0.5 molar ratio(s), as opposed to 1 mole of the intermediate compound (P11′).

The reaction may be also carried out, if necessary, in the presence of an acid or a base and the others.

Examples of the acids to be used in the reaction include organic acids such as acetic acid and inorganic acids such as hydrochloric acid, and examples of the base to be used include tertiary amines such as triethylamine and metal oxide such as magnesium oxide.

The reaction temperature is usually within a range of −20 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are filtered and, if necessary, are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P11). The isolated present fused heterocyclic compound (P11) may be further purified, for example, by chromatography and recrystallization.

(Process 23)

A present fused heterocyclic compound (P12) (when R⁵ represents a —OR¹⁰ group in the formula (1)) can be prepared by reacting the present fused heterocyclic compound (P11) with the compound (M13).

[wherein, R^(10′) represents any group of R¹⁰ defined in the formula (1) other than a hydrogen atom, and each other symbol is the same as defined in the formula (1)]

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include ethers such as THF, ethyleneglycol dimethyl ether, methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; aprotic polar solvents such as DMF, NMP and DMSO; and mixed solvents thereof.

Examples of the base to be used include inorganic bases including an alkali metal or alkaline-earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride; and an alkali metal or alkaline-earth metal carbonates such as sodium carbonate and potassium carbonate; and organic bases such as triethylamine.

In the reaction, the compound (M13) is used usually within a range of 1 to 10 molar ratio(s) and the base is used usually within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P11).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.1 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P12). The isolated present fused heterocyclic compound (P12) may be further purified, for example, by chromatography and recrystallization.

Also, among the present fused heterocyclic compound (P12), the present fused heterocyclic compound (P12) (when R^(10′) represents a trifluoromethyl group) can be carried out according to the below-mentioned process.

[wherein, each symbol is the same as defined in the formula (1)]

The intermediate compound (P11″) can be prepared by reacting the present fused heterocyclic compound (P11) with a base, carbon disulfide and a methylating agent.

The reaction is carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aprotic polar solvents such as DMF, NMP and DMSO.

Examples of the base to be used include alkali metal hydrides such as sodium hydride. Examples of the methylating agent to be used in the reaction include methyl iodide.

In the reaction, the base is used usually within a range of 1 to 2 molar ratio(s), the carbon disulfide is used usually within a range of 1 to 10 molar ratio(s), and the methylating agent is used usually within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the present fused heterocyclic compound (P11).

The reaction temperature is usually within a range of 0 to 100° C. The reaction period of the reaction is usually within a range of 0.5 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P11″). The isolated present fused heterocyclic compound (P11″) may be further purified, for example, by chromatography and recrystallization.

Among the present fused heterocyclic compound (P12), the present fused heterocyclic compound (P12) (when R^(10′) represents a trifluoroethyl group) can be prepared by reacting the intermediate compound (P11″) with a fluorinating agent in the presence of a base.

The reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane.

The reaction is carried out in the presence of a base and a fluorinating agent.

Examples of the base to be used include 1,3-dibromo-5,5-dimethylhydantoin.

Examples of the fluorinating agent to be used in the reaction include tetra-n-butylammonium fluoride and hydrogen fluoride pyridine complex.

In the reaction, the base is used usually within a range of 1 to 10 molar ratio(s), and the fluorinating agent is used usually within a range of 1 to 10 molar ratio(s), as opposed to 1 mole of the intermediate compound (P11″).

The reaction temperature is usually within a range of −80 to 50° C. The reaction period of the reaction is usually within a range of 0.5 to 24 hours.

When the reaction is completed, the reaction mixtures are extracted with organic solvent(s), and the resulting organic layers are worked up (for example, drying and concentration) to isolate the present fused heterocyclic compound (P12) (when R^(10′) represents a trifluoromethyl group). The isolated present fused heterocyclic compound (P12) (when R^(10′) represents a trifluoromethyl group) may be further purified, for example, by chromatography and recrystallization.

(Process 24)

Among the present fused heterocyclic compounds and the above-mentioned intermediate compounds, a reaction between the compounds that includes a nitrogen-containing heterocyclic part having lone pair electrons on nitrogen atom and an oxidizing agent may optionally afford N-oxide compounds having the oxidized nitrogen atom.

Examples of the nitrogen-containing heterocyclic part include a pyridine ring.

The reaction may be carried out according to the well-known method, and typically, may be carried out by using an oxidizing agent such as m-chloroperoxybenzoic acid and hydrogen peroxide in solvent(s) including halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; alcohols such as methanol and ethanol; carboxylic acids such as acetic acid; water; and mixed solvents thereof.

Examples of at least one compound selected from the above-mentioned Group (A) include at least one insecticidal compound selected from the group consisting of clothianidin, thiamethoxam, imidacloprid, nitenpyram, dinotefuran, esfenvalerate, fenpropathrin, lambda-cyhalothrin, fipronil, ethiprole, abamectin, chlorantraniliprole, diamide compound (2b), diamide compound (2c), pymetrozine, pyridalyl, pyriproxyfen, sulfoxaflo, flupyradifurone and spirotetramat.

Imidacloprid, clothianidin, thiamethoxam, dinotefuran, acetamiprid, thiacloprid and nitenpyram to be used herein are all known compounds, and are described, for exmaple, in “The Pesticide Manual-15th edition, published by British Crop Protection Council (BCPC), ISBN 978-1-901396-18-8”, at pages 645, 229, 1112, 391, 9, 1111 and 817 respectively. These compounds are either commercially available, or can be prepared by a known method.

Acrinathrin, bifenthrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, deltamethrin, etofenprox, fenpropathrin, fenvalerate, esfenvalerate, flucythrinate, fluvalinate, tau-fluvalinate, halfenprox, permethrin, silafluofen, tefluthrin, tralomethrin and protrifenbute to be used herein are all known compounds, and also acrinathrin, bifenthrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, deltamethrin, etofenprox, fenpropathrin, fenvalerate, esfenvalerate, flucythrinate, fluvalinate, tau-fluvalinate, halfenprox, permethrin, silafluofen, tefluthrin and tralomethrin and are described, for exmaple, in “The Pesticide Manual-15th edition, published by British Crop Protection Council (BCPC), ISBN 978-1-901396-18-8”, at pages 17, 104, 256, 263, 265, 269, 272, 270, 277, 279, 281, 283, 284, 313, 454, 484, 494, 433, 519, 1236, 562, 598, 879, 1029, 1083 and 1142 respectively. These compounds are either commercially available, or can be prepared by a known method.

Also, protrifenbute is described, for example, in “SHIBUYA INDEX (Index OF Pesticides) 13th edition, 2008, SHIBUYA INDEX RESEARCH GROUP published) ISBN 9784881371435”, at page 28. Protrifenbute is either commercially available, or can be prepared by a known method.

Ethiprole, fipronil, acetoprole, vaniliprole, pyriprole and pyrafluprole to be used herein are all known compounds, and ethiprole and fipronil are described, for example, in “The Pesticide Manual-15th edition, published by British Crop Protection Council (BCPC), ISBN 978-1-901396-18-8”, at pages 443 and 500 respectively. These compounds are either commercially available, or can be prepared by a known method.

Also, acetoprole, vaniliprole, pyriprole and pyrafluprole are described, for example, in “SHIBUYA INDEX (Index OF Pesticides) 13th edition, 2008, SHIBUYA INDEX RESEARCH GROUP published) ISBN 9784881371435”, at page 59. These compounds are either commercially available, or can be prepared by a known method.

Abamectin, emamectin, emamectin benzoate, milbemectine, doramectin and lepimectin to be used herein are all known compounds, and abamectin, emamectin, emamectin benzoate and milbemectine are described, for example, in “The Pesticide Manual-15th edition, published by British Crop Protection Council (BCPC), ISBN 1901396188”, at pages 3, 419, 419 and 793 respectively. These compounds are either commercially available, or can be prepared by a known method. Also, doramectin and lepimectin are described, for example, in “SHIBUYA INDEX (Index OF Pesticides) 13th edition, 2008, SHIBUYA INDEX RESEARCH GROUP published) ISBN 9784881371435”, at pages 66 and 67 respectively. These compounds are either commercially available, or can be prepared by a known method.

Flubendiamide to be used herein is a known compound, and is described, for example, in “The Pesticide Manual-15th edition, published by British Crop Protection Council (BCPC), ISBN 1901396188” at page 514. Said compound is either commercially available, or can be prepared by a known method.

The formula (2)

The compound represented by formula (2) to be used herein, wherein R¹ represents a bromine atom, R² represents a chlorine atom, R³ represents a 1-cyclopropylethyl group and R⁴ represents a hydrogen atom (hereinafter, referred to as “the present diamide compound (2a)” is a known compound, and can be prepared, for example, by a method described in WO 08/280327 pamphlet and the others.

The compound represented by formula (2) to be used herein, wherein R¹ represents a chlorine atom, R² represents a chlorine atom, R¹ and R³ represents both a methyl group and R⁴ represents a hydrogen atom (hereinafter, referred to as “present diamide compound (2b)” is a known compound as chlorantraniliprole, and is described, for example, in “The Pesticide Manual-15th edition, published by British Crop Protection Council (BCPC), ISBN 1901396188”, at page 175. Said compound is either commercially available, or can be prepared by a known method.

The compound represented by formula (2) to be used herein, wherein R¹ and R³ represents both a methyl group, R² represents a cyano group and R⁴ represents a hydrogen atom (hereinafter, referred to as “present diamide compound (2b)” is a known compound and can be prepared, for example, by a method described in WO 06/068669 pamphlet and the others.

The compound represented by formula (2) to be used herein, wherein R¹ and R² represents both a bromine atom, R³ represents a methoxycarbonyl group and R⁴ represents an ethyl group (hereinafter, referred to as present diamide compound (2c)) is a known compound and can be prepared, for example, by a method described in Ser. No. 08/126,933 pamphlet and the others.

Pymetrozine, pyridalyl, pyriproxyfen, spirotetramat, sulfoxaflo and flupyradifurone to be used herein are all known compounds, and pymetrozine, pyridalyl, pyriproxyfen and spirotetramat are described, for example, in “The Pesticide Manual-15th edition, published by British Crop Protection Council (BCPC), ISBN 1901396188”, at pages 968, 988, 997 and 1047 respectively. These compounds are either commercially available, or can be prepared by a known method.

Also, sulfoxaflo represented by the following formula (3) can be prepared, for example, by a method described in WO 2007/095229 pamphlet or and the others.

Also, flupyradifurone represenetd by the following formula (4) is a known compound and can be prepared, for example, by a method described in WO 2007/115644 pamphlet.

Although the composition for controlling pests of the present invention may be a mere mixture of the present fused heterocyclic compound and the present insecticidal compound, the present composition is usually prepared by mixing the present fused heterocyclic compound with the present insecticidal compound and an inert active carrier, and if necessary, adding surfactants and other auxiliary agents for formulation, to formulate into oil solutions, emulsifiable concentrates, flowables, wettable powders, water dispersible granules, dust formulations, granules, microcapsules, aerosols, smoking agents, poison baits, resin formulations, shampoos, paste-like formulations, foams, carbon dioxide formulations and tablets and the others.

Such formulations may be processed into mosquito repellent coils, electric mosquito repellent mats, liquid mosquito formulations, smoking agents, fumigants, sheet formulations, spot-on formulations or formulations for oral treatment.

The composition for controlling pests of the present invention contains usually 0.01 to 95% by weight of the present fused heterocyclic compound.

Also, the above-formulated composition for controlling pests may be used as itself or as the pest-controlling agents with adding other inert ingredients.

In the composition for controlling pests of the present invention, the total amounts of the present fused heterocyclic compounds and the present insecticidal compounds are usually within a range of 0.1 to 100% by weight, preferably within a range of 0.2 to 90% by weight, and more preferably within a range of 1 to 80% by weight.

Examples of the inert carrier to be used in the formulation include an inert solid carrier, an inert liquid carrier and an inert gaseous carrier. Examples of the above-mentioned inert solid carrier include fine powders or granules of clays (for example, kaolin clay, diatomaceous earth, bentonite, Fubasami clay, or acid white clay), synthetic hydrated silicon oxides, talcs, ceramics, other inorganic minerals (for example, sericite, quartz, sulfur, active carbon, calcium carbonate or hydrated silica) or chemical fertilizers (for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea or ammonium chloride) and the others; as well as synthetic resins (for example, polyester resins such as polypropylene, polyacrylonitrile, polymethylmethacrylate and polyethylene terephthalate; nylon resins (for example, nylon-6, nylon-11 and nylon-66); polyamide resins; polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymers, and the others).

Examples of the above-mentioned liquid carriers include water; alcohols (for example, methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol or phenoxy ethanol); ketones (for example, acetone, methyl ethyl ketone or cyclohexanone); aromatic hydrocarbons (for example, toluene, xylene, ethyl benzene, dodecyl benzene, phenyl xylyl ethane or methylnaphthalene); aliphatic hydrocarbons (for example, hexane, cyclohexane, kerosene or light oil); esters (for example, ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyl adipate or propylene glycol monomethyl ether acetate); nitriles (for example, acetonitrile or isobutyronitrile); ethers (for example, diisopropyl ether, 1,4-dioxane, ethyleneglycol dimethyl ether, diethyleneglycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or 3-methoxy-3-methyl-1-butanol); acid aides (for example, N,N-dimethylformamide or N,N-dimethylacetamide); halogenated hydrocarbons (for example, dichloromethane, trichloroethane or carbon tetrachloride); sulfoxides (for example, dimethyl sulfoxide); propylene carbonate; and vegetable oils (for example, soybean oil or cottonseed oil).

Examples of the above-mentioned gaseous carrier include fluorocarbon, butane gas, liquefied petroleum gas (LPG), dimethyl ether, and carbon dioxide gas.

Examples of the surfactants include nonionic surfactants such as polyoxyethylenated alkyl ethers, polyoxyethylenated alkyl aryl ethers and polyethylene glycol fatty acid esters; and anionic surfactants such as alkyl sulfonates, alkylbenzene sulfonates and alkyl sulfates.

Examples of the other auxiliary agents for formulation include a binder, a dispersant and a stabilizer. Specific examples include casein, gelatin, polysaccharides (for example, starch, gum arabic, cellulose derivatives and alginic acid), lignin derivatives, bentonite, water-soluble synthetic polymers (for example, polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acids), PAP (acidic isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

Examples of base material of the resin formulation include polyvinyl chloride polymers, polyurethane and the others, and a plasticizer such as phthalate esters (for example, dimethyl phthalate, dioctyl phthalate), adipic acid esters and stearic acid may be added to these base materials, if necessary. The resin formulation can be prepared by mixing the compound of the present invention with the above-mentioned base material, kneading the mixture, followed by molding it by injection molding, extrusion molding or pressure molding. The resultant resin formulation can be subjected to further molding or cutting procedure, if necessary, to be processed into shapes such as a plate, film, tape, net or string shape. These resin formulations can be processed into animal collars, animal ear tags, sheet products, trap strings, gardening supports and other products.

Examples of a base material for the poison baits include bait ingredients such as grain powder, vegetable oil, saccharide and crystalline cellulose, and if necessary, with addition of antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, accidental ingestion inhibitors for children and pets such as a chili powder, insect attraction fragrances such as cheese flavor, onion flavor and peanut oil.

In the composition for controlling pests of the present invention, the content ratio of the present fused heterocyclic compound to the present insecticidal compound is not specifically limited thereto, and include, for example, usually within a range of 10 to 100,000 parts by weight and preferably within a range of 100 to 10,000 parts by weight, as opposed to 1,000 parts by weight of the present fused heterocyclic compound. That is, the content ratio of the present fused heterocyclic compound to the present insecticidal compound is usually within a range of 100:1 to 1:100 by weight ratio, and preferably within a range of 10:1 to 1:10.

The method for controlling pests of the present invention is usually conducted by applying an effective amount of the composition for controlling pests of the present invention to a pest directly and/or a habitat thereof (for example, plant bodies, soil, the interior of a house, animal bodies). In the method for controlling pests of the present invention, the composition for controlling pests of the present invention is usually in the form of a pest controlling agent.

An effective amount of the composition for controlling pests of the present invention can be applied to plants or soils where the plants are cultivated so as to control the pests. Also, a pre-application treatment into plant seeds or bulbs can also control pests.

Herein, when the composition for controlling pests of the present invention is applied to plants, an effective amount of the composition for controlling pests of the present invention is applied to plants and/or places where the plants grow, plant seeds or bulbs.

Typical examples of an application method of the composition for controlling pests of the present invention include an application to stem and leaf, flower organ or ear of plants (for example, foliage application), an application to nursery (for example, in nursery boxes), an application to the places or soils where plants are cultivated before or after planting, an application to seeds (for example, seed disinfection, seed soaking and seed coating) and an application to bulbs (for example, seed potatoes).

Herein, the plant seeds mean plant seeds in a state before seeding into soils or places where plants are cultivated, and the bulbs means scaly bulbs, solid bulb, root stocks and rhizophore of plants in a state of before planting into soils or places where plants are cultivated.

The pests on which a composition for controlling pests of the present invention has a control efficacy include, for example, harmful insects and harmful mites. The specific examples are follows:

Hemiptera:

Delphacidae (for example, Laodelphax striatellus, Nilaparvata lugens, or Sogatella furcifera),

Deltocephalidae (for example, Nephotettix cincticeps, Nephotettix virescens, or Empoasca onukii),

Aphididae (for example, Aphis gossypii, Myzus persicae, Brevicoryne brassicae, Aphis spiraecola, Macrosiphum euphorbiae, Aulacorthum solani, Rhopalosiphum padi, Toxoptera citricidus, or Hyalopterus pruni),

Pentatomidae (for example, Nezara antennata, Riptortus clavetus, Leptocorisa chinensis, Eysarcoris parvus, or Halyomorpha mista),

Aleyrodidae (for example, Trialeurodes vaporariorum, Bemisia tabaci, Dialeurodes citri, or Aleurocanthus spiniferus),

Coccoidea (for example, Aonidiella aurantii, Comatockaspis perniciosa, Unaspis citri, Ceroplastes rubens, Icerya purchasi, Planococcus Kraunhiae, Pseudococcus longispinis, Pseudaulacaspis Pentagona),

Tingidae,

Cimicoidea (for example, Cimex lectularius, Cimex hemipterus), and

Psyllidae; and the others.

Lepidoptera:

Pyralidae (for example, Chilo suppressalis, Tryporyza Incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella, Ostrinia furnacalis, Hellula undalis, or Pediasia teterrellus),

Noctuidae (for example, Spodoptera litura, Spodoptera exigua, MYthimna separate, bSmestra brassicae, Agrotis ipsilon, Plusia nigrisigna, Trichoplusia spp., Heliothis spp., or Helicoverpa spp.),

Pieridae (for example, Pieris rapae),

Adokisofiesu genus,

Tortricidae (for example, Grapholita molesta, Leguminivora glycinivorella, bntsumuraeses azukivora, Adoxophyes orana fasciata, Adoxophyes honmai., Homona magnanima, Archips fuscocupreanus, or Cydia pomonella).

Gracillariidae (for example, Caloptilia theivora, or Phyllonorycter ringoneella),

Carposinidae (for example, Carposina niponensis),

Lyonetiidae (for example, Lyonetia spp.),

Lymantriidae (for example, Lymantria spp., or Euproctis spp.),

Yponomeutidae (for example, Plutella xylostella),

Gelechiidae (for example, Pectinophora gossypiella, or Phthorimaea operculella),

Arctiidae (for example, Hyphantria cunea), and

Tineidae (for example, Tinea translucens, or Tineola bisselliella); and the others.

Thysanoptera: Frankliniela occidentalis, Thrips pasli, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa, and the others.

Diptera:

House mosquitoes (Culex app.) (for example, Culex pipiens pallens, Culex tritaeniorhynchus, or Culex quinquefasciatus),

Aedes app. (for example, Aedes aegypti, or Aedes albopictus),

Anopheles spp. (for example, Anopheles sinensals),

Chironomidae,

Muscidae (for example, Musca domestica, or Muscina stabulans),

Calliphoridae,

Sarcophagidae,

fanniidae,

Anthomyiidae (for example, Delia platura, or Delia antiqua),

Agromyzidae (for example, Agromyza oryzae, Hydrellia griseola, Liriomysa sativae, Liriomyza trifolii, or Chromatomyia horticola),

Chloropidae (for example, Chlorops oryzae),

Tephritidae (for example, Dacus cucurbitae, or Ceratitis capitata),

Drosophilidaes,

Phoridae (for example, Megaselia spiracularis),

Psychodidae (for example, Clogmia albipunctata),

Sciaridae,

Simuliidae,

Tabanidae (for example, Tabanus trigonus),

Hippoboscidae,

Stomoxyidae, and the others.

Coleoptera:

Corn root worms (Diabrotica spp.) (for example, Diabrotica virgifera virgifera, or Diabrotica undecimpunctata howardi),

Scarabaeidae (for example, Anomala cuprea, Anomala rufocuprea, or Popillia Japonica),

Curculionidae (for example, Sitophilus zeamals, Lissorhoptrus oryzophilus, Callosobruchuys chienensis, Echinocnemus squameus, Anthonomus grandis, or Sphenophorus venatus),

Tenebrionidae (for example, Tenebrio molitor, or Tribolium castaneum),

Chrysomelidae (for example, Oulema oryzae, Aulacophora femoralis, Phyllotreta striolata, or Leptinotarsa decemlineata),

Dermestidae (for example, Anthrenus verbasci, Dennestes maculates),

Anobiidae (for example, Lasioderma serricorne),

Epilachna (for example, Epilachna vigintioctopunctata),

Scolytidae (for example, Lyctus brunneus, or Tomicus piniperda),

Bostrichidae,

Ptinidae,

Cerambycidae (for example, Anoplophora malasiaca),

Elateridae(Agriotes spp.), and

Paederus fuscipes.

Orthoptera:

Locusta migratoria, Gryllotalpa africana, Oxya yezoensis, Oxya japonica, and Grylloidea.

Siphonaptera:

Ctenocephalides fells, Ctenocephalides canis, Pulex Irritans, Xenopsylla cheopis, and the others.

Anoplura:

Pediculus humanus corporis, Phthirus pubis, Haematopinus eurysternus, Dalmalinia ovis, Haematopinus suis, Linognathus setosus and the others.

-   Mallophaga:

Dalmalinia ovis, Dalmalinia bovis, Menopon gallinae, Trichodectes canis, Felicola subrostrata and the others.

Hymenoptera:

Formicidae (for example, Monomorium pharaosis, Formica fusca japonica, Ochetellus glaber, Pristomyrmex pungens, Pheidole noda, Acromyrmex spp., Solenopsis spp., Linepithema humile),

Vespidae,

Betylidae,

Tenthredinidae (for example, Athalia rosae, Athalia japonica).

Blattariae:

Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blatta orientalis, and the others.

Isoptera:

Reticulitermes speratus, Coptotermes formosanus, Incisitermes minor, Cryptotermes domesticus, Odontotermes formosanus, Neotermes koshunensis, Glyptotermes satsumensis, Glyptotermes nakajimai, Glyptotermes fuscus, Glyptotermes kodamai, Glyptotermes kushimensis, Hodotermopsls japonica, Coptotermes guangzhoensis, Reticulitermes miyatakei, Reticulitermes flaviceps amamianus, Reticulitermes sp., Nasutitermes takasagoensis, Pericapritermes nitobei, Sinocapritermes mushae, and the others.

Acarina:

Ixodidae (for example, Haemaphysalis longicorn is, Haemaphysalis flava, Dermacentor taiwanicus, Dermacentor variabilis, fxodes ovatus, Ixodes persulcatus, Ixodes scapularis, Amblyomma americanum, Boophilus mlcroplus, Rhipicephalus sanguineus),

Acaridae (for example, Tyrophagus putrescentiae, or Tyrophagus similis),

Pyroglyphidae (for example, Dermatophagoldes farinae, or Dermatophagoides ptrenyssnus),

Cheyletidae (for example, Cheyletus eruditus, Cheyletus malaccensis, Cheyletus aoorei, or Cheyletiella yasguri),

Sarcoptidae (for example, Octodectes cynotis, or Sacroptes scabiei),

Demodex folliculorum (for example, Demodex canis); Listrophoridae,

Oribatid mites,

Dermanyssidae (for example, Ornithonyssus bacoti, Ornithonyssus sylvairum, or Dermanyssus gallinae),

Trombiculidae (for example, Leptotrombidium akamushi),

Araneae (for example, Chiracanthium japonicum, or Latrodectus hasseltii).

Chilopoda:

Thereuonema hilgendorfi, or Scolopendra subspinipes and the others,

Diplopoda:

Oxidus gracilis, or Nedyopus tambanus and the others, and

Isopoda:

Armadillidium vulgare and the others.

When a composition for controlling pests of the present invention is used for controlling pests in an agricultural field, the application dose as an amount of the present fused heterocyclic compound is usually within a range of 1 to 10,000 g per 10,000 m². The emulsifiable concentrate, the wettable powder, or the flowable formulation etc. of a composition for controlling pests of the present invention is usually applied by diluting it with water in such a way that a concentration of the active ingredient is within a range of 0.01 to 10,000 ppm. The granular formulation, or the dust formulation etc., is usually applied as itself without diluting it.

These formulations or a water dilution thereof can directly be sparged to pests or plants such as crops to be protected from pests, and also can be used to treat the soil of crop land in order to control pests which live there.

When the composition for controlling pests of the present invention is used to control pests that live inside a house, the application dose as an amount of the present fused heterocyclic compound is usually within a range from 0.01 to 1,000 mg per 1 m² of an area to be treated, in the case of using it on a planar area. In the case of using it spatially, the application dose as an amount of the present fused heterocyclic compound is usually within a range of 0.01 to 500 mg per 1 m of the space to be treated. When the composition for controlling pests of the present invention is formulated into emulsifiable concentrates, wettable powders, flowables or the others, such formulations are usually applied after diluting it with water in such a way that a concentration of the active ingredient is within a range of 0.1 to 10,000 ppm, and then sparging it. In the case of being formulated into oil solutions, aerosols, smoking agents, poison baits, resin formulations, shampoos, paste-like formulations, foams, carbon dioxide formulations, tablets, mosquito repellent coils, electric mosquito repellent mats, liquid mosquito formulations, smoking agents, fumigants, sheet formulations, spot-on formulations and formulations for oral treatment, such formulations are used as itself without diluting it.

When the composition for controlling pests of the present invention is used for controlling external parasites of livestock such as cows, horses, pigs, sheep, goats and chickens and small animals such as dogs, cats, rats and mice, the pest control agent of the present invention can be applied to the animals by a known method in the veterinary field. Specifically, when systemic control is intended, the pest control agent of the present invention is administered to the animals as a tablet, a mixture with feed or a suppository, or by injection (including intramuscular, subcutaneous, intravenous and intraperitoneal injections). On the other hand, when non-systemic control is intended, the pest control agent of the present invention is applied to the animals by means of spraying of the oil solution or aqueous solution, pour-on or spot-on treatment, or washing of the animal with a shampoo formulation, or by putting a collar or ear tag made of the resin formulations to the animal. In the case of administering to an animal body, the dose of the present fused heterocyclic compound is usually within a range from 0.1 to 1,000 mg per 1 kg of an animal body weight.

A composition for controlling pests of the present invention can be used in agricultural lands where the following “Plants” are cultivated.

Crops:

-   corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean,     peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco,     and the others;

Vegetables:

-   solanaceous vegetables (for example, eggplant, tomato, pimento,     pepper or potato), -   cucurbitaceous vegetables (for example, cucumber, pumpkin, zucchini,     water melon or melon), -   cruciferous vegetables (for example, Japanese radish, white turnip,     horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard,     broccoli, cauliflower), -   asteraceous vegetables (for example, burdock, crown daisy, artichoke     or lettuce), -   liliaceous vegetables (for example, green onion, onion, garlic or     asparagus), -   ammiaceous vegetables (for example, carrot, parsley, celery or     parsnip), -   chenopodiaceous vegetables (for example, spinach or Swiss chard), -   lamiaceous vegetables (for example, Perilla frutescens, mint or     basil), -   strawberry, sweet potato, Dioscorea japonica, colocasia or the     others;

Fruits:

-   pomaceous fruits (for example, apple, pear, Japanese pear, Chinese     quince or quince), -   stone fleshy fruits (for example, peach, plum, nectarine, Prunus     mume, cherry fruit, apricot or prune), -   citrus fruits (for example, Citrus unshiu, orange, lemon, lime or     grapefruit), -   nuts (for example, chestnut, walnuts, hazelnuts, almond, pistachio,     cashew nuts or macadamia nuts), -   berry fruits (for example, blueberry, cranberry, blackberry or     raspberry), -   grape, kaki persimmon, olive, Japanese plum, banana, coffee, date     palm, coconuts, oil palm and the others;

Trees other than fruit trees:

-   tea, mulberry, -   flowering plant (for example, dwarf azalea, camellia, hydrangea,     sasanqua, Illicium anisatum, cherry trees, tulip tree, crape myrtle     or fragrant olive), -   roadside trees (for example, ash, birch, dogwood, Eucalyptus, Ginkgo     biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar     formosana, plane tree, zelkova, Japanese arborvitae, fir wood,     hemlock, juniper, Pinus, Picea, Taxus cuspidate, elm or Japanese     horse chestnut), Sweet viburnum, Podocarpus macrophyllus, Japanese     cedar, Japanese cypress, croton, Japanese spindletree and Photinia     glabra;

Lawn:

-   sods (for example, Zoysia japonica, Zoysia matrella), bermudagrasses     (for example, Cynodon dactylon), bent glasses (for example, Agrostis     gigantea, Agrostis stolonifera, Agrostis capillaris), -   blueglasses (for example, Poa pratensis, Poe trivialis), festucae     (for example, Festuca arundinacea Schreb., Festuca rubra L. var.     commutata Gaud., Festuca rubra L. var. genuina Hack), -   ryegrassses (for example, Lolium multiflorum Lam, Lolium perenne L), -   Dactylis glomerata, Phleum pratense;

Others:

-   flowers (for example, rose, carnation, chrysanthemum, Eustoma,     gypsophila, gerbera, marigold, salvia, petunia, verbena, tulip,     aster, gentian, lily, pansy, cyclamen, orchid, lily of the valley,     lavender, stock, ornamental cabbage, primula, poinsettia, gladiolus,     cattleya, daisy, cymbidium or begonia), and -   ornamental foliage plants, and the others.

The above-mentioned “Plants” includes genetically modified plants.

EXAMPLES

The following Examples including Production example, Formulation examples, and Test examples serve to illustrate the present invention in more detail, which should not intend to limit the present invention.

Production Examples of the present fused heterocyclic compound are shown below.

Production Example 1 (1)

A mixture of N2-methyl-5-trifluoromethylpyridine-2,3-diamine 0.76 g, 3-fluoropyridine-2-carboaldehyde 0.50 g, sodium hydrogensulfite 0.50 g, and DMF 3 mL was stirred at 120° C. for 8 hr. To the reaction mixture allowed to cool was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-fluoropyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as Intermediate compound (M6-2)) 0.43 g.

Intermediate Compound (M6-2)

¹H-NMR (CDCl₃) δ: 8.75 (1H, d), 8.66-8.63 (1H, m), 8.40 (1H, d), 7.73-7.67 (18, m), 7.56-7.51 (1H, m), 4.16 (3H, s).

Production Example 1 (2)

To a mixture of Intermediate compound (M6-2) 1.23 g and DMF 3.5 mL at ice temperature was added sodium ethanethiolate 0.48 g, and the resulting mixture was stirred at RT for 2 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 1) 1.39 g.

Present Fused Heterocyclic Compound 1

¹H-NMR (CDCl₃) δ: 8.73 (1H, d), 8.53 (1H, dd), 8.39 (1H, d), 7.80 (1H, dd), 7.40 (1H, dd), 4.04 (3H, s), 2.97 (2H, q), 1.35 (3H, t).

Production Examples 2, 3

To a mixture of 2-(3-ethylsulfanylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo ([4,5-b]pyridine (the present fused heterocyclic compound 1) 0.62 g and chloroform 10 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.79 g, and then the resulting mixture was stirred at RT for 5 hr. To the reaction mixture was added saturated aqueous sodium bicarbonate, and the reaction mixture was extracted with chloroform. The organic layer was washed with water, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfinylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 2) 87 mg, and 2-(3-ethylsulfonylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 3) 0.49 g.

Present Fused Heterocyclic Compound 2

¹H-NMR (CDCl₃) δ: 8.85 (1H, dd), 8.77 (1H, s), 8.67 (1H, dd), 8.34 (1H, s), 7.69 (1H, dd), 4.36 (3H, s), 3.72-3.62 (1H, m), 3.14-3.04 (1H, m), 1.47 (3H, t).

Present Fused Heterocyclic Compound 3

¹H-NMR (CDCl₃) δ: 9.01 (1H, dd), 8.76 (1H, s), 8.55 (1H, dd), 8.31 (1H, s), 7.74 (1H, dd), 3.88 (3H, s), 3.83 (2H, q), 1.37 (3H, t).

Production Example 4 (1)

A mixture of N2-methyl-5-trifluoromethylpyridine-2,3-diamine 0.70 g, 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid 0.53 q, EDC hydrochloride 0.82 g, HOBt 42 mg, and pyridine 4.5 mL was stirred at 60° C. for 4 hr. To the reaction mixture allowed to cool was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give Intermediate compound (M20-3).

Intermediate Compound (M20-3)

A mixture of the total amount of the resulting Intermediate compound (M20-3), p-toluenesulfonic acid monohydrate 1.04 g, and N-methylpyrrolidinone 4 mL was stirred with heating at 150° C. for 2.5 hr. To the reaction mixture allowed to cool was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-chloro-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as Intermediate compound (M6-3)) 0.71 g.

Intermediate Compound (M6-3)

¹H-NMR (CDCl₃) δ: 8.96 (1H, d), 8.79 (1H, d), 8.42 (1H, d), 8.22 (1H, d), 4.02 (3H, s).

Production Example 4 (2)

To a mixture of 2-(3-chloro-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (Intermediate compound (M6-3)) 0.71 g and DMF 4 mL at ice temperature was added sodium ethanethiolate 0.24 g, and the resulting mixture was stirred at RT for 1 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 4) 0.76 g.

Present Fused Heterocyclic Compound 4

¹H-NMR (CDCl₃) δ: 8.77 (1H, d), 8.75 (1M, d), 8.43 (1H, d), 7.93 (1H, d), 4.11 (3H, s), 3.02 (2H, q), 1.40 (3H, t).

Production Example 5

To a mixture of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-38-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4) 0.61 g and chloroform 10 mL at ice temperature was added r-chloroperbenzoic acid (65% or more purity) 0.66 g, and then the mixture was stirred at RT for 10 hr. To the reaction mixture was added aqueous 10% sodium thiosulfate and saturated aqueous sodium bicarbonate, and the reaction mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 5) 0.62 g.

Present Fused Heterocyclic Compound 5

¹H-NMR (CDCl₃) δ: 9.25 (1H, d), 8.80 (1H, d), 8.79 (1H, d), 8.34 (1H, d), 3.96 (2H, q), 3.94 (3H, s), 1.42 (3H, t).

Production Example 6

A mixture of 2-(3-ethylsulfanyl-pyridin-2-yl)-6-iodo-3-methyl-3H-imidazo[4,5-b]pyridine 835 mg, sodium pentafluoropropionate 2.0 g, copper iodide 2.0 g, NMP 10 mL, and xylene 50 mL was stirred with heating at 150° C. for 8 hr. The mixture was allowed to cool to RT, and to the mixture was added aqueous 40% ammonia and saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 6) 303 mg.

Present Fused Heterocyclic Compound 6

¹H-NMR (CDCl₃) δ: 8.69 (1H, d), 8.52 (1H, dd), 8.40 (1H, d), 7.80 (1H, dd), 7.39 (1H, dd), 4.06 (3H, s), 2.97 (2H, q), 1.34 (3H, t).

Production Examples 7, 8

To a mixture of 2-(3-ethylsulfanyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine 254 mg and chloroform 10 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 266 mg. The mixture was allowed to warm to RT, and stirred for 0.5 hr. To the mixture was added saturated aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate, and the mixture was extracted with chloroform. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethanesulfinyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 7) 8 mg and 2-(3-ethanesulfonyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 8) 235 rag.

Present Fused Heterocyclic Compound 7

¹H-NMR (CDCl₃) δ: 8.85 (1H, dd), 8.72 (1H, d), 8.68 (1H, dd), 8.31 (1H, d), 7.69 (1H, dd), 4.36 (3H, s), 3.72-3.61 (1H, m), 3.17-3.06 (1H, m), 1.47 (3H, t).

Present Fused Heterocyclic Compound 8

¹H-NMR (CDCl₃) δ: 9.00 (1H, dd), 8.72 (1H, d), 8.55 (1H, dd), 8.30 (1H, d), 7.73 (1H, dd), 3.89 (3H, 3), 3.84 (2H, q), 1.37 (3H, t).

Production Example 9 (1)

To a mixture of 5-iodo-N2-methyl-pyridine-2,3-diamine 1.9 g and pyridine 6 mL was added EDC hydrochloride 1.28 g, HOBt 86 mg, and 3-chloro-pyridine-2-carboxylic acid 1.3 g, and the mixture was stirred at RT for 9 hr. To the reaction mixture was added water, and the precipitated powder was collected by filtration, and washed with chloroform to give 3-chloro-pyridine-2-carboxylic acid (5-iodo-2-methylamino-pyridin-3-yl)-amide (hereinafter referred to as Intermediate compound (M20-7)) 3.6 g.

Intermediate Compound (M20-7)

¹H-NMR (DMSO-D₆) δ: 9.95 (1H, s), 8.65 (1H, d), 8.15-8.10 (2H, m), 8.00 (1H, d), 7.65 (1H, dd), 6.30 (1H, d), 2.81 (3H, d).

Production Example 9 (2)

A mixture of Intermediate compound (M20-7) 3.4 g, p-toluenesulfonic acid monohydrate 5.8 g, DMF 30 mL, and toluene 120 mL was stirred with heating at 130° C. for 12 hr. The mixture was allowed to cool to RT, and to the mixture was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-chloro-pyridin-2-yl)-6-iodo-3-methyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as Intermediate compound (M6-7)) 2.0 g.

Intermediate Compound (M6-7)

¹H-NMR (CDCl₃) δ: 8.70 (1H, d), 8.66-8.63 (1H, m), 8.47-8.44 (1H, m), 7.95 (1H, d), 7.45 (1H, dd), 3.90 (3H, s).

Production Example 9 (3)

A mixture of Intermediate compound (M6-7) 2.0 g, sodium ethanethiolate 888 mg, and DMF 45 mL was stirred with heating at 50° C. for 12 hr. The mixture was allowed to cool to RT, and to the mixture was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-pyridin-2-yl)-6-iodo-3-methyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 9) 1.0 g.

Present Fused Heterocyclic Compound 9

¹H-NMR (CDCl₃) δ: 8.61 (1H, d), 8.51 (1H, dd), 8.45 (1H, d), 7.76 (1H, dd), 7.37 (1H, dd), 3.96 (3H, s), 2.94 (2H, q), 1.33 (3H, t).

Production Example 10 (1)

A mixture of 3-amino-5-trifluoromethylpyridine-2-thiol 0.45 g, 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid 0.55 g, EDC hydrochloride 0.67 g, HOBt 31 mg, and pyridine 4.5 mL was stirred at 60° C. for 4 hr. The reaction mixture was allowed to cool, and to the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give Intermediate compound (M20-9).

Intermediate Compound (M20-9)

A mixture of the total amount of the resulting Intermediate compound (M20-9), p-toluenesulfonic acid monohydrate 1.04 g, and N-methylpyrrolidinone 3.5 mL was stirred with heating at 150° C. for 2 hr. To the reaction mixture allowed to cool was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-chloro-5-trifluoromethylpyridin-2-yl)-6-(trifluoromethyl)thiazolo[5,4-b]pyridine (hereinafter referred to as Intermediate compound (M6-9)) 0.29 g.

Intermediate Compound (M6-9)

¹H-NMR (CDCl₃) δ: 8.94 (1H, d), 8.90 (1H, d), 8.69 (1H, d), 8.19 (1H, d).

Production Example 10 (2)

2-(3-Ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-6-(trifluoromethyl)thiazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 10) was prepared in a similar manner as described for the preparation of Production example 4 (2) by using Intermediate compound (M6-9) instead of 2-(3-chloro-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (Intermediate compound (M6-3)).

Present Fused Heterocyclic Compound 10

¹H-NMR (CDCl₃) δ: 8.91 (1H, d), 8.70-8.67 (2H, m), 7.91 (1H, s), 3.09 (2H, q), 1.51 (3H, t).

Production Example 11

2-(3-Ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-6-(trifluoromethyl)thiazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 11) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-6-(trifluoromethyl) thiazolo[5,4-b]pyridine instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 11

¹H-NMR (CDCl₃) δ: 9.19 (1H, d), 8.98 (1H, d), 8.89 (1H, d), 8.61 (1H, d), 4.17 (2H, q), 1.49 (3H, t).

Production Example 12 (1)

A mixture of 3-amino-5-trifluoromethylpyridine-2-thiol 0.45 g, 3-chloropyridine-2-carboxylic acid 0.39 g, EDC hydrochloride 0.67 g, HOBt 31 mg, and pyridine 4 mL was stirred at RT for 12 hr. To the reaction mixture was added water, and the precipitated solid was collected by filtration. The resulting solid was washed with water, and n-hexane, and dried to give 3-chloropyridine-2-carboxylic acid (2-mercapto-5-trifluoromethylpyridin-3-yl)-amide (hereinafter referred to as Intermediate compound (M20-11)) 0.45 g.

Intermediate Compound (M20-11)

Production Example 12 (2)

A mixture of Intermediate compound (M20-11) 0.45 q, p-toluenesulfonic acid monohydrate 0.70 g, and NMP 4 mL was stirred at 150° C. for 2 hr. To the reaction mixture allowed to cool was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-chloropyridin-2-yl)-6-(trifluoromethyl)thiazolo[5,4-b]pyridine (hereinafter referred to as Intermediate compound (M6-11)) 0.47 g.

Intermediate Compound (M6-11)

Production Example 12 (3)

2-(3-Ethylsulfanyl-2-yl)-6-(trifluoromethyl)thiazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 41) was prepared in a similar manner as described for the preparation of Production example 1 (2) by using Intermediate compound (M6-11) instead of 2-(3-fluoropyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (Intermediate compound (M6-2)).

Present Fused Heterocyclic Compound 41

¹H-NMR (CDCl₃) δ: 8.87 (1H, d), 8.64 (1H, d), 8.48 (18, dd), 7.76 (1H, dd), 7.37 (1H, dd), 3.06 (2H, q), 1.49 (3H, t).

Production Example 12 (4)

To a mixture of 2-(3-ethylsulfanyl-2-yl)-6-(trifluoromethyl)thiazolo[5,4-b]pyridine 0.36 g and chloroform 5 mL was added m-chloroperbenzoic acid (65% or more purity) 0.56 g, and the resulting mixture was stirred at RT for 12 hr. To the reaction mixture was added aqueous 10% sodium thiosulfate and saturated aqueous sodium bicarbonate, and the mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 2-(3-ethylsulfonyl-2-yl)-6-(trifluoromethyl)thiazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 12) 0.27 g and 2-(3-ethylsulfonyl-2-yl)-6-(trifluoromethyl)thiazolo[5,4-b]pyridine 4-oxide (hereinafter referred to as the present fused heterocyclic compound 22) 91 mg.

Present Fused Heterocyclic Compound 12

¹H-NMR (CDCl₃) δ: 8.98-8.93 (2H, m), 8.66 (1H, dd), 8.57 (1H, d), 7.69 (1H, dd), 4.13 (2H, q), 1.45 (3H, t).

Present Fused Heterocyclic Compound 22

¹H-NMR (CDCl₃) δ: 8.96 (1H, dd), 8.68 (1H, dd), 8.62 (1H, s), 8.20 (1H, s), 7.74 (1H, dd), 4.06 (2H, q), 1.44 (3H, t).

Production Example 13 (1)

A mixture of 2-(3-ethylsulfanyl-pyridin-2-yl)-6-iodo-3-methyl-3H-imidazo[4,5-b]pyridine 1.1 g, copper iodide 160 mg, sodium sulfide nonahydrate 2.7 g, and DMF 10 mL was stirred at 110° C. for 5 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give the compound having the formula:

(hereinafter referred to as Intermediate compound (P9′-1)) 710 mg.

Intermediate Compound (P9′-1)

¹H-NMR (DMSO-D₆) δ: 8.56-8.55 (2H, m), 8.53-8.50 (2H, m), 8.38-8.36 (2H, m), 8.04 (2H, d), 7.61-7.56 (2H, m), 3.87 (6H, brs), 3.00 (4H, q), 1.23-1.16 (6H, m).

Production Example 13 (2)

A mixture of Intermediate compound (P9′-1) 710 mg and DMF 12 mL was cooled to −60° C., and to the mixture was added trifluoroiodomethane 10 g. To the mixture was added dropwise tetrakis(dimethylamino)ethylene 1.2 mL at −40° C. The mixture was allowed to warm to −10° C. and stirred at −10° C. for 5 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 13) 530 mg.

Present Fused Heterocyclic Compound 13

¹H-NMR (CDCl₃) δ: 8.67 (1H, d), 8.52 (1H, dd), 8.46 (1H, d), 7.79 (1H, dd), 7.39 (1H, dd), 4.03 (3H, s), 2.97 (2H, q), 1.36 (3H, t).

Production Examples 14, 15

A mixture of 2-(3-ethylsulfanyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 13) 200 mg, m-chloroperbenzoic acid (65% or more purity) 230 mg, and chloroform 10 mL was stirred at ice temperature for 5 hr. To the reaction mixture was added saturated aqueous sodium bicarbonate, and the mixture was extracted with chloroform. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfinyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 14) 89 mg and 2-(3-ethylsulfonyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 15) 130 mg.

Present Fused Heterocyclic Compound 14

¹H-NMR (CDCl₃) δ: 8.87-8.83 (1H, m), 8.73-8.64 (2H, m), 8.41 (1H, d), 7.72-7.66 (1H, m), 4.34 (3H, s), 3.72-3.62 (1H, m), 3.17-3.05 (1H, m), 1.47 (3H, t).

Present Fused Heterocyclic Compound 15

¹H-NMR (CDCl₃) δ: 9.01-8.98 (1H, m), 8.71 (1K, d), 8.55-8.52 (1H, m), 8.39 (1H, d), 7.72 (1H, dd), 3.90-3.81 (5H, m), 1.36 (3H, t).

Production Example 16

To a mixture of 2-(3-ethylsulfanyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 13) 270 mg, sodium tungstate dihydrate 110 mg, and acetonitrile 5 mL was added aqueous 30% hydrogen peroxide 2 mL at 40° C. The mixture was heated to 80° C. and stirred for 24 hr. To the mixture was added saturated aqueous sodium thiosulfate, and then the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfonyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 16) 280 mg.

Present fused heterocyclic compound 16

¹H-NMR (CDCl₃) δ: 9.08 (1H, d), 9.04 (1H, dd), 8.71 (1H, d), 8.57 (1H, dd), 7.79 (1H, dd), 3.93 (3H, s), 3.82 (2H, q), 1.38 (3H, t).

Production Example 17(1)

A mixture of N2-methyl-5-pentafluoroethyl-pyridine-2,3-diamine 590 mg, 3-chloro-5-trifluoromethyl-pyridine-2-carboxylic acid 560 mg, EDC hydrochloride 520 ag, HOBt 35 mg, pyridine 5 mL was stirred at RT for 5 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure to give Intermediate compound (M20-17).

Intermediate Compound (M20-17)

The resulting Intermediate compound (M20-17) was dissolved in a mixed solvent of DMF 7.5 mL and toluene 30 mL, and to the resulting mixture was added p-toluenesulfonic acid monohydrate 1.5 g. The mixture was stirred at 160° C. for 6 hr. The reaction mixture allowed to cool to RT, and to the reaction mixture was added saturated aqueous sodium bicarbonate, and then the mixture was extracted with t-butyl methyl ether. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-chloro-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as Intermediate compound (M6-17)) 540 mg.

Intermediate Compound (M6-17)

¹H-NMR (CDCl₃) δ: 8.96 (1H, d), 8.74 (1H, d), 8.40 (1H, d), 8.23 (1H, d), 4.03 (3H, s).

Production Example 17(2)

2-(3-Ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 17) was prepared in a similar manner as described for the preparation of Production example 1 (2) by using Intermediate compound (M6-17) instead of 2-(3-fluoropyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (Intermediate compound (M6-2)).

Present Fused Heterocyclic Compound 17

1H-NMR (CDCl₃) δ: 8.75 (1H, d), 8.71 (1H, d), 8.42 (1H, d), 7.93 (1H, d), 4.12 (3H, s), 3.03 (2H, q), 1.41 (3H, t).

Production Examples 18, 19

2-(3-Ethylsulfinyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 18) and 2-(3-ethylsulfonyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 19) was prepared in a similar manner as described for the preparation of Production examples 2, 3 by using 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3-imidazo[4,5-b]pyridine instead of 2-(3-ethylsulfanylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 1).

Present Fused Heterocyclic Compound 18

¹H-NMR (CDCl₃) δ: 9.10 (1H, d), 8.94 (1H, d), 8.76 (1H, d), 8.36 (1H, d), 4.41 (3H, s), 3.76-3.66 (1H, m), 3.18-3.07 (1H, m), 1.49 (3H, t).

Present Fused Heterocyclic Compound 19

¹H-NMR (CDCl₃) δ: 9.27 (1H, d), 8.80 (1H, d), 8.76 (1H, s), 8.34 (1H, s), 4.01-3.94 (5H, m), 1.41 (3H, t).

Production Example 20

To a mixture of 2-(3-ethylsulfonyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3-imidazo[4,5-b]pyridine 500 mg and chloroform 10 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 429 mg, and the mixture was stirred at RT for 1 hr and at 50° C. for 2 hr. To the reaction mixture was added aqueous sodium thiosulfate and aqueous sodium bicarbonate, and the mixture was extracted with chloroform. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfinyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 20) 353 mg.

Present Fused Heterocyclic Compound 20

¹H-NMR (CDCl₃) δ: 9.02 (1H, dd), 8.77 (1H, d), 8.60-8.52 (2H, m), 7.75 (1H, dd), 3.91 (3H, s), 3.83 (2H, q), 1.38 (3H, t).

Production Example 21 (1)

To a mixture of 4-iodo-2-nitro-phenylamine 2.0 g, 60% sodium hydride (in oil) 330 mg, DMF 20 mL at ice temperature was added dropwise iodomethane 470 μL. The reaction mixture was allowed to warm to RT, and then stirred for 2 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give (4-iodo-2-nitro-phenyl)-methyl-amine 2.0 q.

Production Example 21 (2)

A mixture of iron powder 1.7 g, acetic acid 2.2 mL, ethanol 80 mL, and water 25 mL was stirred at 70° C. To the reaction mixture was added dropwise a mixture of (4-iodo-2-nitro-phenyl)-methyl-amine 2.0 g and ethanol 20 mL. After adding dropwise, the mixture was stirred at 70° C. for 6 hr. The reaction mixture was filtered washing with THF. The resulting filtrate was concentrated under reduced pressure. To the resultant residue was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 4-iodo-N1-methyl-benzene-1,2-diamine 1.6 g.

Production Example 21 (3)

A mixture of 4-iodo-N-methyl-benzene-1,2-diamine 850 mg, 3-chloro-pyridine-2-carboxylic acid 590 mg, EDC hydrochloride 790 mg, HOBt 46 mg, and pyridine 10 mL at 100° C. for 12 hr was stirred. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-chloro-pyridin-2-yl)-5-iodo-1-methyl-1H-benzimidazole (hereinafter referred to as Intermediate compound (M6-21)) 930 mg.

Intermediate Compound (M6-21)

Production Example 21 (4)

2-(3-Ethylsulfanyl-pyridin-2-yl)-5-iodo-1-methyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 21) was prepared in a similar manner as described for the preparation of Production example 1 (2) by using Intermediate compound (M6-21) instead of 2-(3-fluoropyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (Intermediate compound (M6-2)).

Present Fused Heterocyclic Compound 21

1H-NMR (CDCl₃) δ: 8.49 (1H, dd), 8.22 (1H, d), 7.75 (1H, d), 7.62 (18, dd), 7.35 (1H, dd), 7.21 (1H, d), 3.87 (3H, s), 2.92 (2H, q), 1.32 (3H, t).

Production Example 22 (1)

A mixture of 4-aminophenylsulfurpentafluoride 5.2 g, acetic anhydride 2.7 mL, triethylamine 6.6 mL, and chloroform 20 mL was stirred at RT for 3 hr. To the mixture was added water, and the reaction mixture was extracted with chloroform. The resultant residue was recrystallized by using hexane and ethyl acetate to give 4-acetamidephenyl sulfur pentafluoride 5.4 g.

Production Example 22 (2)

To a mixture of 4-acetamidephenyl sulfur pentafluoride 5.4 g and sulfuric acid 15 mL at ice temperature was added dropwise fuming nitric acid 905 mL. After adding dropwise, the mixture was stirred at RT for 3 hr. To ice was poured the reaction mixture, the precipitated crystal was collected by filtration. The crystal was washed with water and dried to give 4-amino-3-nitrophenyl sulfur pentafluoride 5.2 g.

Production Example 22 (3)

To a mixture of 4-amino-3-nitrophenyl sulfur pentafluoride 2.0 g, 60% sodium hydride (in oil) 310 mg and DMF 15 mL at ice temperature was added dropwise iodomethane 447 μL. After adding dropwise, the mixture was stirred at RT for 3 hr. To water was poured the reaction mixture, and then the precipitated solid was collected by filtration. The solid was washed with water and dried to give methyl-(2-nitro-4-pentafluorosulfanyl-phenyl)-amine 2.0 g.

¹H-NMR (CDCl₃) δ: 8.60 (1H, d), 8.28 (1H, brs), 7.78 (1H, dd), 6.89 (1H, d), 3.10 (3H, d).

Production Example 22 (4)

N1-Methyl-4-pentafluorosulfanyl-benzene-1,2-diamine was prepared in a similar manner as described for the preparation of Production example 21 (2) by using methyl-(2-nitro-4-pentafluorosulfanyl-phenyl)-amine instead of (4-iodo-2-nitro-phenyl)-methyl-amine.

Production Example 22 (5)

3-Chloro-pyridine-2-carboxylic acid (2-methylamino-5-pentafluorosulfanyl-phenyl)-amide (hereinafter referred to as Intermediate compound (M20-23)) was prepared in a similar manner as described for the preparation of Production example 9 (1) by using N1-methyl-4-pentafluorosulfanyl-benzene-1,2-diamine instead of 5-iodo-N2-methyl-pyridine-2,3-diamine.

Intermediate Compound (M20-23)

¹H-NMR (CDCl₃) δ: 9.57 (1H, s), 8.55 (1H, dd), 7.91 (1H, dd), 7.81 (1H, d), 7.59 (1H, dd), 7.50-7.45 (1H, m), 6.71 (1H, d), 4.52 (1H, d), 2.93 (3H, d).

Production Example 22 (6)

To a mixture of Intermediate compound (M20-23) 405 mg and DMF 10 mL at ice temperature was added sodium ethanethiolate 193 mg, and then the mixture was stirred at RT for 8 hr and at 60° C. for 2 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-pentafluorosulfanyl-1-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 23) 411 mg.

Present Fused Heterocyclic Compound 23

¹H-NMR (CDCl₃) δ: 8.50 (1H, dd), 8.33 (1H, d), 7.79-7.74 (2H, m), 7.46-7.43 (1H, m), 7.37 (1H, dd), 3.92 (3H, s), 2.94 (2H, q), 1.33 (3H, t).

Production Example 23

2-(3-Ethylsulfonyl-pyridin-2-yl)-1-methyl-5-pentafluorosulfanyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 24) was prepared in a similar manner as described for the preparation of Production example 11 by using 2-(3-ethylsulfanyl-pyridin-2-yl)-1-methyl-5-pentafluorosulfanyl-1H-benzimidazole instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 24

¹H-NMR (CDCl₃) δ: 8.96 (1H, dd), 8.50 (1H, dd), 8.24 (1H, d), 7.79 (1H, dd), 7.68 (1H, dd), 7.48 (1H, d), 3.82 (2H, q), 3.75 (3H, 5), 1.34 (3H, t).

Production Example 24 (1)

3-Chloro-5-trifluoromethyl-pyridine-2-carboxylic acid (5-iodo-2-methylamino-pyridin-3-yl)-amide (hereinafter referred to as Intermediate compound (M20-35)) was prepared in a similar manner as described for the preparation of Production example 9 (1) by using 3-chloro-5-trifluoromethyl-pyridine-2-carboxylic acid instead of 3-chloro-pyridine-2-carboxylic acid.

Intermediate Compound (M20-35)

¹H-NMR (CDCl₃) δ: 9.33 (1H, s), 8.80 (1H, d), 8.28 (1H, d), 8.17 (1H, d), 8.00 (1H, d), 4.60 (1H, s), 3.01 (3H, d).

Production Example 24 (2)

2-(3-Chloro-5-trifluoromethyl-pyridin-2-yl)-6-iodo-3-methyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as Intermediate compound (M6-35)) was prepared in a similar manner as described for the preparation of Production Example 9 (2) by using Intermediate compound (M20-35) instead of 3-chloro-pyridine-2-carboxylic acid (5-iodo-2-methylamino-pyridin-3-yl)-amide (Intermediate compound (M20-7)).

Intermediate Compound (M6-35)

¹H-NMR (CDCl₃) δ: 8.95 (1H, s), 8.68 (1H, s), 8.49 (1H, s), 8.20 (1H, s), 3.95 (3H, s).

Production Example 24 (3)

2-(3-Ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-6-iodo-3-methyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 42) was prepared in a similar manner as described for the preparation of Production example 1 (2) by using Intermediate compound (M6-35) instead of 2-(3-fluoropyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (Intermediate compound (M6-2)).

Present Fused Heterocyclic Compound 42

¹H-NMR (CDCl₃) δ: 8.73 (1H, s), 8.65 (1H, d), 8.49 (1H, d), 7.91 (1H, s), 4.04 (3H, s), 3.01 (2H, q), 1.39 (3H, t).

Production Example 24 (4)

A mixture of 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-6-iodo-3-methyl-3H-imidazo[4,5-b]pyridine 900 mg, thiobenzoic acid 320 μL, copper iodide 45 mg, 1,10-phenanthroline 85 mg, diisopropylethylamine 940 μL, and toluene 25 mL was stirred at 110° C. for 8 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give thiobenzoic acid S-[2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-3H-imidazo[4,5-b]pyridine]ester 990 mg.

¹H-NMR (CDCl₃) δ: 8.74 (1H, s), 8.54 (1H, d), 8.33 (1H, d), 8.07 (2H, dd), 7.92 (1H, s), 7.63 (1H, t), 7.51 (2H, t), 4.10 (3H, a), 3.01 (2H, q), 1.39 (3H, t).

Production Example 24 (5)

A mixture of thiobenzoic acid S-[2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-3H-imidazo[4,5-b]pyridine]ester 1.8 g, potassium carbonate 1.1 g, and methanol 20 mL was stirred at RT for 4.5 hr. To the reaction mixture was added saturated aqueous ammonium chloride, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate, dried over sodium sulfate, and concentrated under reduced pressure to give 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-3H-imidazo[4,5-b]pyridine-6-thiol (hereinafter referred to as the present fused heterocyclic compound 43) 1.2 g.

Present Fused Heterocyclic Compound 43

¹H-NMR (CDCl₃) δ: 8.73 (1H, s), 8.46 (1H, d), 8.19 (1H, d), 7.90 (1H, s), 4.04 (3H, s), 3.01 (2H, q), 1.39 (3H, t).

Production Example 24 (6)

A mixture of 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-3-imidazo[4,5-b]pyridine-6-thiol 1.2 g, iodine 20 mg, and DMF 30 mL was stirred at RT for 12 hr under air atmosphere. The reaction mixture was concentrated, and the resultant residue was treated with silica gel column chromatography to give a compound having the formula:

(hereinafter referred to as Intermediate compound (P9′-4)) 800 mg.

Intermediate Compound (P9′-4)

¹H-NMR (CDCl₃) δ: 8.73 (2H, s), 8.52 (2H, d), 8.35 (2H, d), 7.91 (2H, d), 4.06 (6H, s), 3.04-2.98 (4H, m), 1.39 (6H, t).

Production Example 24 (7)

2-(3-Ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 28) was prepared in a similar manner as described for the preparation of Production example 13 (2) by using Intermediate compound (P9′-4) instead of Intermediate compound (P9′-1).

Present Fused Heterocyclic Compound 28

¹H-NMR (CDCl₃) δ: 8.75 (1H, d), 8.71 (1H, d), 8.50 (1H, d), 7.93 (1H, d), 4.10 (3H, s), 3.03 (2H, q), 1.41 (3H, t).

Production Example 24 (8)

To a mixture of 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine 299 mg and chloroform 30 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.34 g, and the mixture was stirred at ice temperature for 5 hr. To the reaction mixture was added saturated aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate, and the reaction mixture was extracted with chloroform. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 44) 0.24 g.

Present Fused Heterocyclic Compound 44

¹H-NMR (CDCl₃) δ: 9.24 (1H, d), 8.79 (1H, d), 8.74 (1H, d), 8.40 (1H, d), 3.97 (2H, q), 3.93 (3H, s), 1.42 (3H, t).

Production Example 24 (9)

2-(3-Ethylsulfonyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfonyl-3-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 25) was prepared in a similar manner as described for the preparation of Production example 16 by using 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine instead of 2-(3-ethylsulfanyl-pyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 13).

Present Fused Heterocyclic Compound 25

¹H-NMR (CDCl₃) δ: 9.28 (1H, d), 9.10 (1H, d), 8.80 (1H, d), 8.72 (1H, d), 3.98 (3H, s), 3.93 (2H, q), 1.43 (3H, t).

Production Example 25

A mixture of 2-(3-ethylsulfanyl-pyridin-2-yl)-5-iodo-1-methyl-1H-benzimidazole 340 mg, copper iodide 410 mg, sodium pentafluoropropionate 800 mg, NMP 5 mL, xylene 5 mL was stirred at 160° C. for 5 hr. The reaction mixture was allowed to cool to RT, and then to the reaction mixture was added saturated aqueous sodium bicarbonate and aqueous 28% ammonia, and the mixture was extracted with t-butyl methyl ether. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-pyridin-2-yl)-1-methyl-5-pentafluoroethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 26) 240 mg.

Present Fused Heterocyclic Compound 26

¹H-NMR (CDCl₃) δ: 8.50 (1H, dd), 8.16 (1H, s), 7.77 (1H, dd), 7.57 (1H, d), 7.53 (1H, d), 7.36 (1H, dd), 3.93 (3H, s), 2.94 (2H, q), 1.33 (3H, t).

Production Example 26

2-(3-Ethylsulfonyl-pyridin-2-yl)-1-methyl-5-pentafluoroethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 27) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanyl-pyridin-2-yl)-1-methyl-5-pentafluoroethyl-1H-benzimidazole instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 27

¹H-NMR (CDCl₃) δ: 8.98 (18, dd), 8.53 (1H, dd), 8.06 (1H, s), 7.70 (1H, dd), 7.60 (1H, d), 7.56 (1H, d), 3.86-3.78 (5H, m), 1.34 (3H, t).

Production Example 27

To a mixture of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine 0.18 g and chloroform 4 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.21 g, and the mixture was stirred at ice temperature for 5 min. To the reaction mixture was added saturated aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate, and the reaction mixture was extracted with chloroform. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethylsulfanyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 29) 0.16 g.

Present Fused Heterocyclic Compound 29

¹H-NMR (CDCl₃) δ: 9.10-9.07 (1H, m), 8.94-8.91 (1H, m), 8.77-8.74 (1H, m), 8.46-8.44 (1H, m), 4.38 (3H, s), 3.76-3.65 (1H, m), 3.16-3.05 (1H, m), 1.49 (3H, t).

Production Example 28 (1)

3-Chloro-pyridine-2-carboxylic acid (2-methylamino-5-trifluoromethyl-phenyl)-amide (hereinafter referred to as Intermediate compound (M20-29)) was prepared in a similar manner as described for the preparation of Production example 9 (1) by using N1-methyl-4-trifluoromethyl-benzene-1,2-diamine instead of 5-iodo-N2-methyl-pyridine-2,3-diamine.

Intermediate Compound (M20-29)

¹H-NMR (CDCl₃) δ: 9.56 (1H, s), 8.55-8.54 (1H, m), 7.91 (1H, dd), 7.70 (1H, d), 7.49-7.43 (3H, m), 6.79 (1H, d), 2.93 (3H, d).

Production Example 28 (2)

A mixture of Intermediate compound (M20-29) 800 mg, sodium ethanethiolate 350 mg, and DMF 10 mL was stirred at 100° C. for 5 hr. To the reaction mixture was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-pyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 30) 410 mg.

Present Fused Heterocyclic Compound 30

¹H-NMR (CDCl₃) δ: 8.51 (1H, dd), 8.17 (1H, d), 7.78 (1H, dd), 7.61 (1H, dd), 7.52 (1H, d), 7.38 (1H, dd), 3.93 (3H, s), 2.94 (2H, q), 1.33 (3H, t).

Production Examples 29, 30

2-(3-Ethylsulfinyl-pyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 31) and 2-(3-ethylsulfonyl-pyridine-2-yl)-1-methyl-5-trifluoromethyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 32) were prepared in a similar manner as described for the preparation of Production examples 2, 3 by using 2-(3-ethylsulfanyl-pyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benzimidazole instead of 2-(3-ethylsulfanylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine.

Present Fused Heterocyclic Compound 31

¹H-NMR (CDCl₃) δ: 8.77 (1H, d), 8.61 (1H, d), 8.05 (1H, s), 7.61 (1H, dd), 7.55 (1H, d), 7.48 (1H, d), 4.20 (3H, s), 3.73-3.61 (1H, m), 3.11-3.00 (1H, m), 1.47 (3H, t).

Present Fused Heterocyclic Compound 32

¹H-NMR (CDCl₃) δ: 8.95 (1H, dd), 8.50 (1H, dd), 8.09 (1H, d), 7.66 (1H, dd), 7.61 (1H, d), 7.53 (1H, d), 3.83 (2H, q), 3.75 (3H, s), 1.33 (3H, t).

Production Example 31 (1)

3-Chloro-5-trifluoromethyl-pyridine-2-carboxylic acid (2-methylamino-5-trifluoromethyl-phenyl)-amide (hereinafter referred to as Intermediate compound (M20-31)) was prepared in a similar manner as described for the preparation of Production example 9 (1) by using N1-methyl-4-trifluoromethyl-benzene-1,2-diamine instead of 5-iodo-N2-methyl-pyridine-2,3-diamine and by using 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid instead of 3-chloro-pyridine-2-carboxylic acid.

Intermediate Compound (M20-31)

¹H-NMR (CDCl₃) δ: 9.42 (1H, s), 8.80 (1H, d), 8.16 (1H, d), 7.71 (1H, s), 7.47 (1H, d), 6.81 (1H, d), 4.32 (1H, s), 2.93 (3H, d).

Production Example 31 (2)

2-(3-Ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 33) and 3-ethylsulfanyl-5-trifluoromethyl-pyridine-2-carboxylic acid (2-methylamino-5-trifluoromethyl-phenyl)-amide (hereinafter referred to as Intermediate compound (M3-32)) was prepared in a similar manner as described for the preparation of Production example 28 (2) by using Intermediate compound (M20-31) instead of 3-chloro-pyridine-2-carboxylic acid (2-methylamino-5-trifluoromethyl-phenyl)-amide (Intermediate compound (M20-29)).

Present Fused Heterocyclic Compound 33

¹H-NMR (CDCl₃) δ: 8.72 (1H, d), 8.21 (1H, d), 7.91 (1H, d), 7.63 (1H, d), 7.54 (1H, d), 4.00 (3H, s), 3.00 (2H, q), 1.38 (3H, t).

Intermediate Compound (M3-32)

¹H-NMR (CDCl₃) δ: 9.64 (1H, s), 8.53 (1H, d), 7.86 (1H, s), 7.76 (1H, d), 7.41 (1H, dd), 6.76 (1H, d), 4.35 (1H, d), 2.96 (2H, q), 2.90 (3H, d), 1.44 (3H, t).

Production Examples 32, 33

2-(3-Ethylsulfinyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 34) and 2-(3-ethylsulfonyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benz imidazole (hereinafter referred to as the present fused heterocyclic compound 35) was prepared in a similar manner as described for the preparation of Production examples 2, 3 by using 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benzimidazole instead of 2-(3-ethylsulfanylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 1).

Present Fused Heterocyclic Compound 34

¹H-NMR (CDCl₃) δ: 9.05 (1H, d), 8.91 (1H, d), 8.12 (1H, d), 7.67 (1H, dd), 7.60 (1H, d), 4.32 (3H, s), 3.80-3.70 (1H, m), 3.15-3.05 (1H, m), 1.51 (3H, t).

Present Fused Heterocyclic Compound 35

¹H-NMR (CDCl₃) δ: 9.22 (1H, d), 8.77 (1H, d), 8.10 (1H, d), 7.66 (1H, dd), 7.57 (1H, d), 3.98 (2H, q), 3.84 (3H, s), 1.40 (3H, t).

Production Examples 34, 35

To a mixture of 2-(3-ethylsulfonylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine 550 mg and chloroform 15 mL was added m-chloroperbenzoic acid (65% or more purity) 750 mg, and the mixture was heated to reflux for 20 hr. To the reaction mixture was added aqueous 10% sodium thiosulfate, and the reaction mixture was extracted with chloroform. The organic layer was washed with saturated aqueous sodium bicarbonate, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-1-oxypyridin-2-yl)-3-methyl-6-trifluoromethyl-3-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 36) 168 mg and 2-(3-ethylsulfonylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine 4-oxide (hereinafter referred to as the present fused heterocyclic compound 37) 73 mg.

Present Fused Heterocyclic Compound 36

¹H-NMR (CDCl₃) δ: 8.79 (1H, d), 8.54 (1H, dd), 8.33 (1H, d), 7.99 (1H, dd), 7.69 (1H, dd), 3.85-3.74 (4H, m), 3.52-3.42 (1H, m), 1.34 (3H, t).

Present Fused Heterocyclic Compound 37

¹H-NMR (CDCl₃) δ: 9.03 (1H, dd), 8.53 (1H, dd), 8.47 (1H, d), 7.92 (1H, d), 7.77 (1H, dd), 4.29 (3H, s), 3.69 (2H, q), 1.36 (3H, t).

Production Example 36 (1)

2-(3-Chloro-5-trifluoromethyl-pyridin-2-yl)-5-iodo-1-methyl-1H-benzimidazole (hereinafter referred to as Intermediate compound (M6-41)) was prepared in a similar manner as described for the preparation of Production example 4 (1) by using 4-iodo-N1-methyl-benzene-1,2-diamine instead of N2-methyl-5-trifluoromethylpyridine-2,3-diamine.

Intermediate Compound (M6-41)

¹H-NMR (CDCl₃) δ: 8.92 (1H, d), 8.23 (1H, d), 8.17 (1H, d), 7.66 (1H, dd), 7.23 (1H, d), 3.85 (3H, s).

Production Example 36 (2)

2-(3-Ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-5-iodo-1-methyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 45) was prepared in a similar manner as described for the preparation of Production example 1 (2) by using Intermediate compound (M6-41) instead of 2-(3-fluoropyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine.

Present Fused Heterocyclic Compound 45

Production Example 36 (3)

2-(3-Ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-pentafluoroethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 38) was prepared in a similar manner as described for the preparation of Production example 25 by using 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-5-iodo-1-methyl-1H-benzimidazole instead of 2-(3-ethylsulfanyl-pyridin-2-yl)-5-iodo-1-methyl-1H-benzimidazole.

Present Fused Heterocyclic Compound 38

¹H-NMR (CDCl₃) δ: 8.72 (1H, d), 8.20 (1H, s), 7.91 (1H, d), 7.60 (1H, d), 7.55 (1H, d), 4.00 (3H, s), 3.01 (2H, q), 1.39 (3H, t).

Production Examples 37, 38

2-(3-Ethylsulfinyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-pentafluoroethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 39) and 2-(3-ethylsulfonyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-pentafluoroethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 40) was prepared in a similar manner as described for the preparation of Production examples 2, 3 by using 2-(3-ethylsulfanyl-5-trifluoromethyl-pyridin-2-yl)-1-methyl-5-pentafluoroethyl-1H-benzimidazole instead of 2-(3-ethylsulfanylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine.

Present Fused Heterocyclic Compound 39

¹H-NMR (CDCl₃) δ: 9.05 (1H, d), 8.91 (1H, d), 8.10 (1H, s), 7.66-7.60 (2H, m), 4.33 (3H, s), 3.80-3.69 (1H, m), 3.17-3.07 (1H, m), 1.50 (3H, t).

Present Fused Heterocyclic Compound 40

¹H-NMR (CDCl₃) δ: 9.22 (1H, d), 8.77 (1H, d), 8.08 (1H, s), 7.63 (1H, d), 7.58 (1H, d), 3.99 (2H, q), 3.84 (3H, s), 1.40 (3H, t).

Production Example 39 (1)

To a mixture of methyl-(2-nitro-4-trifluoromethyl-phenyl)-amine 16 g and acetonitrile 200 mL at ice temperature was added N-bromosuccinimide 15 g. The reaction mixture was stirred at RT for 5 hr. To the resulting reaction mixture was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give (2-bromo-6-nitro-4-trifluoromethyl-phenyl)-methyl-amine 15 g.

(2-bromo-6-nitro-4-trifluoromethyl-phenyl)-methyl-amine

¹H-NMR (CDCl₃) δ: 8.12 (1H, s), 7.86 (1H, s), 6.48 (1H, brs), 3.07 (3H, d).

Production Example 39 (2)

While a mixture of iron powder 11 g, acetic acid 12 mL, THF 40 mL, and water 10 mL was stirred with heating at 70° C., to the mixture was added dropwise another mixture of (2-bromo-6-nitro-4-trifluoromethyl-phenyl)-methyl-amine 10 g and THF 50 mL. After adding dropwise, the mixture was stirred with heating at 70° C. for 3 hr. The resulting reaction mixture was filtered using Celite (Trademark) with washing with THF. The resulting filtrate was concentrated under reduced pressure. To the resultant residue was added aqueous 10% sodium hydroxide, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure to give 3-bromo-N2-methyl-5-trifluoromethyl-benzene-1,2-diamine 11 g.

3-Bromo-N2-methyl-5-trifluoromethyl-benzene-1,2-diamine

Production Example 39 (3)

3-Chloro-pyridine-2-carboxylic acid (3-bromo-2-methylamino-5-trifluoromethyl-phenyl)-amide (hereinafter referred to as Intermediate compound (M20-43)) was prepared in a similar manner as described for the preparation of Production example 9 (1) by using 3-bromo-N2-methyl-5-trifluoromethyl-benzene-1,2-diamine instead of 5-iodo-N2-methyl-pyridine-2,3-diamine.

Intermediate Compound (M20-43)

¹H-NMR (CDCl₃) δ: 10.63 (1H, s), 8.77 (1H, d), 8.58 (1H, dd), 7.91 (1H, dd), 7.56 (1H, d), 7.47 (1H, dd), 3.75-3.68 (1H, m), 2.83 (3H, d).

Production Example 39 (4)

2-(3-Ethylsulfanyl-pyridin-2-yl)-7-bromo-1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 75), 3-ethylsulfanyl-pyridine-2-carboxylic acid (3-bromo-2-methylamino-5-trifluoromethyl-phenyl)-amide (hereinafter referred to as Intermediate compound (M3-42)), and 2-(3-chloro-pyridin-2-yl)-7-bromo-1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as Intermediate compound (M6-43)) were prepared in a similar manner as described for the preparation of Production example 28 (2) by using Intermediate compound (M20-43) instead of Intermediate compound (M20-29).

Present Fused Heterocyclic Compound 75

¹H-NMR (CDCl₃) δ: 8.54 (1H, dd), 8.08 (1H, d), 7.79 (1H, dd), 7.72 (1H, d), 7.40 (1H, dd), 4.13 (3H, s), 2.94 (2H, q), 1.32 (3H, t).

Intermediate Compound (M3-42)

¹H-NMR (CDCl₃) δ: 10.80 (1H, s), 8.82 (1H, s), 8.38 (1H, dd), 7.74 (1H, d), 7.54 (1H, s), 7.42 (1H, dd), 3.75-3.65 (1H, brm), 2.97 (2H, q), 2.82 (3H, d), 1.45 (3H, t).

Intermediate Compound (M6-43)

¹H-NMR (CDCl₃) δ: 8.71 (1H, dd), 8.08 (1H, d), 7.95 (1H, dd), 7.74 (1H, d), 7.47 (1H, dd), 4.09 (3H, s).

Production Example 40

2-(3-Ethylsulfonyl-pyridin-2-yl)-7-bromo-1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 46) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanyl-pyridin-2-yl)-7-bromo-1-methyl-5-trifluoromethyl-1H-benzimidazole instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 46

¹H-NMR (CDCl₃) δ: 8.99 (1H, dd), 8.51 (1H, dd), 8.00 (1H, d), 7.75 (1H, d), 7.72 (1H, dd), 4.03 (3H, s), 3.73 (2H, q), 1.33 (3H, t).

Production Examples 41, 42

A mixture of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4) 1.0 g, m-chloroperbenzoic acid (65% or more purity) 2.72 g, and chloroform 5 mL was refluxed for 8 hr, and to the mixture was added m-chloroperbenzoic acid (65% or more purity) 2.0 g, and then the mixture was further refluxed for 5 hr. To the reaction mixture allowed to cool was added aqueous 10% sodium thiosulfate, and the reaction mixture was extracted with chloroform. The organic layer was washed with saturated aqueous sodium bicarbonate, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine 4-oxide (hereinafter referred to as the present fused heterocyclic compound 48) 362 mg and 2-(3-ethylsulfonyl-1-oxy-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 51) 45 mg.

Present Fused Heterocyclic Compound 48

¹H-NMR (CDCl₃) δ: 9.27 (1H, d), 8.76 (1H, d), 8.49 (1H, d), 7.94 (1H, d), 4.33 (3H, s), 3.80 (2H, q), 1.40 (3H, t).

Present Fused Heterocyclic Compound 51

¹H-NMR (CDCl₃) δ: 8.75 (1H, s), 8.50 (1H, s), 8.12 (1H, s), 7.94 (1H, s), 4.28 (3H, s), 3.75-3.65 (1H, m), 3.55-3.44 (1H, m), 1.38 (3H, t).

Production Example 43 (1)

A mixture of 2-chloro-3-nitro-5-trifluoromethylpyridine 2.60 g, 2,2,2-trifluoroethylamine 0.79 g, N,N-diisopropylethylamine 1.04 g, and N-methyl-2-pyrrolidone 5 mL was stirred at RT for 10 hr. To the reaction mixture was added aqueous 10% citric acid, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over sodium sulfate, and then concentrated under reduced pressure to give (3-nitro-5-trifluoromethylpyridin-2-yl)-(2,2,2-trifluoroethyl)amine 1.83 g.

(3-Nitro-5-trifluoromethylpyridin-2-yl)-(2,2,2-trifluoroethyl)amine

¹H-NMR (CDCl₃) δ: 8.72 (1H, d), 8.68 (1H, d), 8.59 (1H, brs), 4.54-4.41 (2H, m).

Production Example 43 (2)

To a mixture of iron powder 2.12 g, ethanol 6 mL, water 4 mL, and acetic acid 0.1 mL was added dropwise another mixture of (3-nitro-5-trifluoromethylpyridin-2-yl)-(2,2,2-trifluoroethyl)amine 1.83 g and ethanol 10 mL at 70° C., and then the resulting mixture was stirred at 70° C. for 1 hr. The reaction mixture allowed to cool was filtered, and then the filtrate was extracted with ethyl acetate and water. The organic layer was washed with water, and dried over sodium sulfate, and then concentrated under reduced pressure to give N2-(2,2,2-trifluoroethyl)-5-trifluoromethylpyridine-2,3-diamine 1.59 g.

N2-(2,2,2-Trifluoroethyl)-5-trifluoromethylpyridine-2,3-diamine

¹H-NMR (CDCl₃) δ: 8.04-8.02 (1H, m), 7.10-7.07 (1H, m), 4.81 (1H, brs), 4.31-4.20 (2H, m), 3.34 (2H, brs).

Production Example 43 (3)

A mixture of N2-(2,2,2-trifluoroethyl)-5-trifluoromethylpyridine-2,3-diamine 0.52 g, 3-ethylsulfanylpyridine-2-carboxylic acid 0.37 g, EDC hydrochloride 0.46 g, HOBt 27 mg, and pyridine 2 mL was stirred at RT for 3 hr. To the reaction mixture was added aqueous 10% citric acid, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over sodium sulfate, and then concentrated under reduced pressure to give 3-ethylsulfanylpyridine-2-carboxylic acid [2-(2,2,2-trifluoroethyl)amino-5-trifluoromethylpyridin-3-yl]amide (hereinafter referred to as Intermediate compound (M3-43)) 0.75 g.

Intermediate Compound (M3-43)

Production Example 43 (4)

A mixture of Intermediate compound (M3-43) 0.75 g and acetic acid 5 mL was stirred with heating to reflux for 2 days. The mixture was cooled to RT, and then concentrated under reduced pressure. The crude product was treated with silica gel column chromatography to give 2-(3-ethylsulfanylpyridin-2-yl)-3-(2,2,2-trifluoroethyl)-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 65) 0.53 g.

Present Fused Heterocyclic Compound 65

¹H-NMR (CDCl₃) δ: 8.77-8.74 (1H, m), 8.48 (1H, dd), 8.45-8.42 (1H, m), 7.82 (1H, dd), 7.40 (1H, dd), 5.64 (2H, q), 2.99 (2H, q), 1.35 (3H, t).

Production Example 44 (1)

A mixture of N2-(2,2,2-trifluoroethyl)-5-trifluoromethylpyridine-2,3-diamine 0.52 g, 3-ethylsulfanyl-5-trifluoromethylpyridine-2-carboxylic acid 0.50 g, EDC hydrochloride 0.46 g, HOBt 27 mg, and pyridine 2 mL was stirred at RT for 3 hr. To the reaction mixture was added aqueous 10% citric acid, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over sodium sulfate, and then concentrated under reduced pressure to give 3-ethylsulfanyl-5-trifluoromethylpyridine-2-carboxylic acid [2-(2,2,2-trifluoroethyl)amino-5-trifluoromethylpyridin-3-yl]amide (hereinafter referred to as Intermediate compound (M3-44)) 0.89 g.

Intermediate Compound (M3-44)

Production Example 44 (2)

A mixture of Intermediate compound (M3-44) 0.89 g, p-toluenesulfonic acid•monohydrate 1.14 g, N-methyl-2-pyrrolidone 10 mL, and xylene 10 mL was heated to reflux for 8 hr with removing water using Dean-Stark apparatus. The reaction mixture was allowed to cool, and then to the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water, and dried over sodium sulfate, and then concentrated under reduced pressure. The crude product was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-(2,2,2-trifluoroethyl)-6-trifluoromethyl-3H-imidazo 4,5-b)pyridine (hereinafter referred to as the present fused heterocyclic compound 66) 0.76 g.

Present Fused Heterocyclic Compound 66

¹H-NMR (CDCl₃) δ: 8.80 (1H, d), 8.70 (1H, d), 8.48 (1H, d), 7.96 (1H, d), 5.67 (2H, q), 3.04 (2H, q), 1.40 (3H, t).

Production Example 45

To a mixture of the present fused heterocyclic compound 65 0.32 g and chloroform 2 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.36 g, and then the mixture was allowed to warm to RT, and stirred for 1 hr. To the mixture was added saturated aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate, and the reaction mixture was extracted with chloroform. The organic layer was washed with water, and dried over sodium sulfate, and then concentrated under reduced pressure. The crude product was treated with silica gel column chromatography to give 2-(3-ethylsulfonylpyridin-2-yl)-3-(2,2,2-trifluoroethyl)-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 67) 0.32 g.

Present Fused Heterocyclic Compound 67

¹H-NMR (CDCl₃) δ: 8.98 (1H, dd), 8.80 (1H, d), 8.59 (1H, dd), 8.37 (1H, d), 7.75 (1H, dd), 5.31 (2H, q), 3.95 (2H, q), 1.40 (3H, t).

Production Example 46

To a mixture of the present fused heterocyclic compound 66 (0.32 g) and chloroform 2 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.31 g, and then the mixture was allowed to warm to RT, and stirred for 1 hr. To the mixture was added saturated aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate, and the reaction mixture was extracted with chloroform. The organic layer was washed with water, and dried over sodium sulfate, and then concentrated under reduced pressure. The resulting crude product was washed with hexane to give 2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-(2,2,2-trifluoroethyl)-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 68) 0.28 g.

Present Fused Heterocyclic Compound 68

¹H-NMR (CDCl₃) δ: 9.22 (1H, d), 8.83-8.83 (2H, m), 8.40 (1H, d), 5.36 (2H, q), 4.05 (2H, q), 1.45 (3H, t).

Production Example 47 (1)

A mixture of 2-chloro-5-iodopyridine 20.0 g, sodium pentafluoropropionate 77.8 g, copper iodide (I) 31.8 g, xylene 84 mL, and N-methylpyrrolidone 84 mL was heated to 160° C., and stirred with heating to reflux for 6 hr. The reaction mixture was cooled to RT, and then to the reaction mixture was added water. The mixture was extracted with methyl-tert-butyl ether. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure to give 2-chloro-5-pentafluoroethylpyridine.

2-Chloro-5-pentafluoroethylpyridine

¹H-NMR (CDCl₃) δ: 8.65-8.62 (1H, m), 7.85-7.81 (1H, m), 7.48-7.44 (1H, m)

Production Example 47 (2)

A mixture of a half amount of 2-chloro-5-pentafluoroethylpyridine prepared in Production example 47 (1), zinc cyanide (II) 14.4 g, tetrakis(triphenylphosphine)palladium 2.42 g, and N-methylpyrrolidone 84 mL was heated to 80° C., and stirred with heating for 2.5 hr. The reaction mixture was cooled to RT, and then to the mixture was added water and methyl-tert-butyl ether. The mixture was filtrated with Celite (Trademark) to remove the resulting precipitate, and the resultant residue was washed with methyl-tert-butyl ether. The filtrate was extracted with methyl-tert-butyl ether, and the organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The crude product was treated with silica gel column chromatography to give 2-cyano-5-pentafluoroethylpyridine 4.19 g.

2-Cyano-5-pentafluoroethylpyridine

¹H-NMR (CDCl₃) δ: 8.97-8.96 (1H, m), 8.12-8.09 (1H, m), 7.90-7.87 (1H, m)

Production Example 47 (3)

A mixture of water 17 mL and concentrated sulfuric acid 17 mL was heated to 100° C., and to the mixture was added dropwise 2-cyano-5-pentafluoroethylpyridine 3.81 g with heating, and then the mixture was stirred at 100° C. for 2.5 hr. The mixture was cooled to RT, and then the reaction mixture was added to iced water. The precipitated solid was collected by filtration, and washed with water. The resulting solid was dried under reduced pressure to give 5-pentafluoropyridine-2-carboxylic acid 3.52 g.

5-Pentafluoropyridine-2-carboxylic acid

¹H-NMR (CDCl₃) δ: 8.92-8.88 (1H, m), 8.44-8.39 (1H, m), 8.25-8.20 (1H, m)

Production Example 47 (4)

A mixture of tetramethylpiperidine 5.5 mL and THF 58 mL was cooled to −78° C., and then a solution of 1.6 M n-butyllithium in hexane was added dropwise into the mixture. The mixture was allowed to warm to RT, and then stirred for 10 min. The mixture was cooled to −78° C. again, and to the mixture was added dropwise a solution of 5-pentafluoropyridine-2-carboxylic acid 3.52 g in THF, and the mixture was stirred at −78° C. for 1 hr. To the mixture was added dropwise diethyldisulfide 4.0 mL at −78° C. Then the mixture was allowed to warm to RT and was stirred for 1 hr. To the reaction mixture was added 1N hydrochloric acid, and then to the mixture was added aqueous 5 N sodium hydroxide. The aqueous layer was washed with methyl-tert-butyl ether. To the aqueous layer was added 12 N hydrochloric acid, and the precipitated solid was collected by filtration and dissolved in methyl-tert-butyl ether. The mixture was dried over sodium sulfate, and then concentrated under reduced pressure to give 3-ethylsulfanyl-5-pentafluoroethylpyridine-2-carboxylic acid (hereinafter referred to as Intermediate compound (M2-7)) 1.99 g.

Intermediate Compound (M2-7)

¹H-NMR (CDCl₃) δ: 8.51-8.50 (1H, m), 7.89-7.87 (1H, m), 3.01 (2H, q), 1.46 (3H, t)

Production Example 47 (5)

A mixture of N2-methyl-5-trifluoromethylpyridine-2,3-diamine 0.50 g, Intermediate compound (M2-7) 0.79 g, EDC hydrochloride 0.37 g, HOBt 35 mg, and pyridine 5 mL was stirred at RT for 3 hr. To the reaction mixture was added water, and the mixture was extracted with methyl-tert-butyl ether. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure to give 3-ethylsulfanyl-5-pentafluoroethylpyridine-2-carboxylic acid (2-methylamino-5-trifluoromethylpyridin-3-yl)amide (hereinafter referred to as Intermediate compound (M3-45)).

Intermediate Compound (M3-45)

¹H-NMR (CDCl₃) δ: 9.57 (1H, bra), 8.54-8.52 (1H, m), 8.37-8.35 (1H, m), 7.94-7.92 (1H, m), 7.89-7.87 (1H, m), 4.97 (1H, brs), 3.08 (3H, d), 2.99 (2H, q), 1.45 (3H, t)

A mixture of the total amount of the resulting Intermediate compound (M3-45) and acetic acid 5 mL was heated to 120° C., and stirred with heating to reflux for 3 hr. The mixture was cooled to RT, and then concentrated under reduced pressure. The crude product was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-5-pentafluoroethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 71) 0.77 g.

Present Fused Heterocyclic Compound 71

¹H-NMR (CDCl₃) δ: 8.78-8.76 (1H, m), 8.71-8.69 (1H, m), 8.44-8.42 (1H, m), 7.91-7.89 (1H, m), 4.13 (3H, s), 3.02 (2H, q), 1.39 (3H, t)

Production Example 48

To a mixture of the present fused heterocyclic compound 71 0.47 g and chloroform 10 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.57 g, and then the mixture was allowed to warm to RT and stirred for 1 hr. To the mixture was added saturated aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate, and the reaction mixture was extracted with chloroform. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The crude product was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-5-pentafluoroethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 72) 0.39 g.

Present Fused Heterocyclic Compound 72

¹H-NMR (CDCl₃) δ: 9.21-9.19 (1H, m), 8.81-8.79 (1H, m), 8.76-8.75 (1H, m), 8.35-8.33 (1H, m), 3.99-3.93 (5H, m), 1.41 (3H, t)

Production Example 49

A mixture of N2-methyl-5-pentafluoroethylpyridine-2,3-diamine 0.50 g, Intermediate compound (M2-7) 0.62 g, EDC hydrochloride 0.29 g, HOBt 28 mg, and pyridine 4 mL was stirred at RT for 3 hr. To the reaction mixture was added water, and the mixture was extracted with methyl-tert-butyl ether. The organic layer was dried over magnesium sulfate, and then concentrated under reduced pressure to give 3-ethylsulfanyl-5-pentafluoroethylpyridine-2-carboxylic acid (2-methylamino-5-pentafluoroethylpyridin-3-yl)amide (hereinafter referred to as Intermediate compound (M3-46)).

Intermediate Compound (M3-46)

¹H-NMR (CDCl₃) δ: 9.59 (1H, bra), 8.54-8.52 (1H, m), 8.32-8.30 (1H, m), 7.89-7.87 (1H, m), 7.85-7.83 (1H, m), 5.04 (1H, brs), 3.09 (3H, d), 2.99 (2H, q), 1.45 (3H, t)

A mixture of the total amount of the resulting Intermediate compound (M3-46) and acetic acid 4 mL was heated to 120° C. and stirred with heating to reflux for 3 hr. The mixture was cooled to RT, and then concentrated under reduced pressure. The crude product was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-5-pentafluoroethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 73) 0.84 g.

Present Fused Heterocyclic Compound 73

¹H-NMR (CDCl₃) δ: 8.72-8.69 (2H, m), 8.42-8.41 (1H, m), 7.90-7.89 (1H, m), 4.15-4.12 (3H, m), 3.02 (2H, q), 1.40 (3H, t)

Production Example 50

To a mixture of the present fused heterocyclic compound 73 0.54 g and chloroform 11 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.59 g, and then the mixture was allowed to warm to RT and stirred for 1 hr. To the mixture was added saturated aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate, and the reaction mixture was extracted with chloroform. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure.

The crude product was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-5-pentafluoroethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 74) 0.34 g.

Present Fused Heterocyclic Compound 74

¹H-NMR (CDCl₃) δ: 9.21-9.20 (1H, m), 8.77-8.74 (2H, m), 8.32-8.31 (1H, m), 4.00-3.94 (5H, m), 1.41 (3H, t)

Production Example 51

2-(3-Ethylsulfonylpyridin-2-yl)-1-methyl-5-trifluoromethoxy-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 50) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanylpyridin-2-yl)-1-methyl-5-trifluoromethoxy-1H-benzimidazole instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 50

¹H-NMR (CDCl₃) δ: 8.93 (18, dd), 8.49 (1H, dd), 7.68-7.62 (2H, m), 7.43 (1H, d), 7.25 (1H, d), 3.84 (2H, q), 3.73 (3H, s), 1.31 (3H, q).

Production Example 52

2-(3-Ethylsulfonylpyridin-2-yl)-5-trifluoromethyl-benzothiazole (hereinafter referred to as the present fused heterocyclic compound 53) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanylpyridin-2-yl)-5-trifluoromethyl-benzothiazole instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 53

¹H-NMR (CDCl₃) δ: 8.92 (1H, dd), 8.65 (1H, dd), 8.37 (1H, s), 8.11 (1H, d), 7.72 (1H, dd), 7.66 (1H, dd), 4.19 (2H, q), 1.45 (3H, t).

Production Example 53

2-(3-Ethylsulfonylpyridin-2-yl)-6-trifluoromethyl-oxazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 81) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanylpyridin-2-yl)-6-trifluoromethyl-oxazolo[5,4-b]pyridine instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 81

¹H-NMR (CDCl₃) δ: 9.06 (1H, dd), 8.79 (1H, d), 8.58 (1H, dd), 8.43 (1H, d), 7.78 (1H, dd), 3.88 (2H, q), 1.44 (3H, t).

Production Example 54

2-(3-Ethylsulfonylpyridin-2-yl)-5-trifluoromethyl-benzoxazole (hereinafter referred to as the present fused heterocyclic compound 85) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanylpyridin-2-yl)-5-trifluoromethyl-benzoxazole instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 85

¹H-NMR (CDCl₃) δ: 9.03 (1H, dd), 8.60 (1H, dd), 8.16-8.13 (1H, m), 7.82-7.71 (3H, m), 4.01 (2H, q), 1.43 (3H, t).

Production Example 55

To phosphorus oxychloride 2.04 g at ice temperature was added the present fused heterocyclic compound 48 (0.20 g), and the mixture was stirred at 110° C. for 2 hr. The reaction mixture was allowed to cool to RT, and to the reaction mixture at ice temperature was added saturated aqueous sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 5-chloro-2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 89) 0.21 g.

Present Fused Heterocyclic Compound 89

¹H-NMR (CDCl₃) δ: 9.25 (1H, d), 8.78 (1H, d), 8.43 (1H, s), 3.97-3.87 (5H, m), 1.41 (3H, t).

Production Example 56

To a mixture of the present fused heterocyclic compound 89 (0.20 g) and NMP 0.5 mL was added dimethylamine (in methanol, 2.0 mol/L) 0.3 mL, and the mixture was stirred at RT for 1 hr and at 50° C. for 3 hr. To the reaction mixture allowed to cool to RT was added dimethylamine (in methanol, 2.0 mol/L) 0.3 mL, and the mixture was stirred at 50° C. for 3 hr. To the reaction mixture allowed to cool to RT was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 5-dimethylamino-2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 99) 0.03 g.

Present Fused Heterocyclic Compound 99

¹H-NMR (CDCl₃) δ: 9.20 (1H, d), 8.76 (1H, d), 8.26 (1H, s), 4.02 (2H, q), 3.84 (3H, s), 3.04 (6H, s), 1.41 (3H, t).

Production Example 57

7-Cyano-2-(3-ethylsulfonylpyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 130) was prepared in a similar manner as described for the preparation of Production example 5 by using 7-cyano-2-(3-ethylsulfanylpyridin-2-yl)-1-methyl-5-trifluoromethyl-1H-benzimidazole instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 130

¹H-NMR (CDCl₃) δ: 9.02 (1H, dd), 8.54 (1H, dd), 8.28 (1H, s), 7.95 (1H, s), 7.77 (1H, dd), 4.06 (3H, s), 3.74 (2H, q), 1.35 (3H, t).

Production Example 58

2-(5-Chloro-3-ethylsulfonylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 312) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(5-chloro-3-ethylsulfanylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-oromethyl-3-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 312

¹H-NMR (CDCl₃) δ: 8.95 (1H, d), 8.72-8.71 (1H, m), 8.53 (1H, d), 8.30-8.28 (1H, m), 3.94-3.87 (5H, m), 1.40 (3H, t)

To a mixture of the present fused heterocyclic compound 48 (0.30 g), triethylamine 0.14 mL, and acetonitrile 1 mL, trimethylsilyl cyanide 0.35 mL was added, and the mixture was stirred at 110° C. for 3 hr. To the reaction mixture allowed to cool to RT was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 5-cyano-2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 399) 0.23 g.

Present Fused Heterocyclic Compound 399

¹H-NMR (CDCl₃) δ: 9.28 (1H, d), 8.79 (1H, d), 8.48 (1H, s), 3.96 (3H, s), 3.89 (2H, q), 1.42 (3H, t).

Production Example 60

To a mixture of 2-(3-ethylsulfanylpyridin-2-yl)-1-methyl-7-methylsulfanyl-5-trifluoromethyl-1-benzimidazole 0.11 g and chloroform 5 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.32 g, and then the resulting mixture was stirred at RT for 5 hr. The reaction mixture was cooled at ice temperature, and to the mixture was added m-chloroperbenzoic acid (65% or more purity) 0.32 g, and then the mixture was stirred at RT for 3 hr. To the reaction mixture was added aqueous 10% sodium thiosulfate and saturated aqueous sodium bicarbonate, and the reaction mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 2-(3-ethylsulfonylpyridin-2-yl)-1-methyl-7-methylsulfonyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present fused heterocyclic compound 404) 0.62 g.

Present Fused Heterocyclic Compound 404

¹H-NMR (CDCl₃) δ: 9.08-8.97 (1H, m), 8.58-8.46 (1H, m), 8.41-8.26 (2H, m), 7.84-7.70 (1H, m), 4.12 (3H, s), 3.72-3.59 (2H, m), 3.33 (3H, s), 1.39-1.22 (3H, m).

Production Example 61

To a mixture of the present fused heterocyclic compound 19 (2.0 g) and chloroform 20 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 3.03 g, and then the mixture was stirred with heating to reflux for 3 hr. The reaction mixture was cooled at ice temperature, and to the mixture was added m-chloroperbenzoic acid (65% or more purity) 3.03 g, and then the mixture was stirred with heating to reflux for 3 hr. The reaction mixture was cooled at ice temperature, and to the mixture was added m-chloroperbenzoic acid (65% or more purity) 3.03 g, and then the mixture was stirred with heating to reflux for 3 hr. To the reaction mixture allowed to cool to RT was added aqueous 10% sodium thiosulfate and saturated aqueous sodium bicarbonate, and the reaction mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 2-(3-ethylsulfonyl-5-trifluoromethyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine 4-oxide (hereinafter referred to as the present fused heterocyclic compound 409) 1.10 g.

Present Fused Heterocyclic Compound 409

¹H-NMR (CDCl₃) δ: 9.27 (1H, d), 8.77 (1H, d), 8.45 (1H, s), 7.92 (1H, s), 4.34 (3H, s), 3.81 (2H, q), 1.40 (3H, t).

Production Example 62

To a mixture of the present fused heterocyclic compound 19 (0.65 g), methanol 6 mL, THF 6 mL, and water 2 mL was added sodium hydroxide 0.54 g, and the mixture was stirred with heating to reflux for 1 day. To the reaction mixture allowed to cool to RT was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-5-trimethoxymethyl-pyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 414) 0.25 g.

Present Fused Heterocyclic Compound 414

¹H-NMR (CDCls) δ: 9.16 (1H, d), 8.74 (1H, d), 8.70 (1H, d), 8.31 (1H, d), 3.93 (3H, s), 3.88 (2H, q), 3.28 (9H, s), 1.38 (3H, t).

Production Example 63

2-(3-Methylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 419) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-methylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 419

¹H-NMR (CDCl₃) δ: 9.25 (1H, s), 8.85 (1H, s), 8.75 (1H, s), 8.32 (1H, s), 3.96 (3H, s), 3.73 (3H, s)

Production Example 64

2-(3-Propylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 421) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-propylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 421

¹H-NMR (CDCl₃) δ: 9.24 (1H, s), 8.79 (1H, s), 8.74 (1H, s), 8.31 (1H, s), 3.95-3.88 (5H, m), 1.92-1.81 (2H, m), 1.13 (3H, t)

Production Example 65

2-(3-Isopropylsulfonyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 423) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-isopropylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-pentafluoroethyl-3H-imidazo[4,5-b]pyridine instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 423

¹H-NMR (CDCl₃) δ: 9.24 (1H, s), 8.75 (2H, d), 8.31 (1H, s), 4.71-4.60 (1H, m), 3.93 (3H, s), 1.39 (6H, d)

Production Example 66

2-(3-Ethylsulfonylpyridin-2-yl)-6-pentafluoroethyl-oxazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 464) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanylpyridin-2-yl)-6-pentafluoroethyl-oxazolo[5,4-b]pyridine instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 464

¹H-NMR (CDCl₃) δ: 9.07 (1H, dd), 8.74 (1H, d), 8.59 (1H, dd), 8.41 (1H, d), 7.80 (1H, dd), 3.91 (2H, q), 1.45 (3H, t).

Production Example 67

2-(3-Ethylsulfonylpyridin-2-yl)-5-pentafluoroethyl-benzoxazole (hereinafter referred to as the present fused heterocyclic compound 467) was prepared in a similar manner as described for the preparation of Production example 5 by using 2-(3-ethylsulfanylpyridin-2-yl)-5-pentafluoroethyl-benzoxazole instead of 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-3-methyl-6-trifluoromethyl-3H-imidazo[4,5-b]pyridine (the present fused heterocyclic compound 4).

Present Fused Heterocyclic Compound 467

¹H-NMR (CDCl₃) δ: 9.04 (1H, dd), 8.61 (1H, dd), 8.12 (1H, d), 7.82 (1H, d), 7.75 (1H, dd), 7.72 (1H, dd), 4.04 (2H, q), 1.44 (3H, t).

Production Example 68 (1)

A mixture of 2-amino-4-(trifluoromethylsulfanyl)phenol 1.0 g, 3-ethylsulfanylpicolinic acid 0.87 g, EDC hydrochloride 1.10 g, and chloroform 10 mL was stirred at RT for 30 min. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 3-ethylsulfanyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide 1.32 g.

3-Ethylsulfanyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide

¹H-NMR (CDCl₃) δ: 10.40 (1H, brs), 9.63 (1H, s), 8.36 (1H, dd), 7.75 (1H, dd), 7.53 (1H, d), 7.45 (1H, dd), 7.41 (1H, dd), 7.08 (1H, d), 2.97 (2H, q), 1.44 (3H, t).

Production Example 68 (2)

A mixture of 3-ethylsulfanyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide 1.23 q, di-2-methoxyethyl azodicarboxylate (hereinafter referred to as DMEAD) 1.28 g, triphenylphosphine 1.39 g, and THF 30 mL was stirred at RT for 1 hr and at 50° C. for 1 hr. The reaction mixture allowed to cool to RT was concentrated under reduced pressure, and to the mixture was added water. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanylpyridin-2-yl)-5-(trifluoromethylsulfanyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 441) 1.21 g.

Present Fused Heterocyclic Compound 441

¹H-NMR (CDCl₃) δ: 8.59 (1H, dd), 8.27 (1H, s), 7.78 (1H, dd), 7.75-7.69 (2H, m), 7.42 (1H, dd), 3.07 (2H, q), 1.47 (3H, t).

Production Example 69

To a mixture of the present fused heterocyclic compound 441 (1.06 g) and chloroform 30 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 1.47 g, and then the mixture was stirred at RT for 6 hr. To the reaction mixture was added aqueous 10% sodium sulfite, and the reaction mixture was extracted with chloroform. The organic layer was washed with saturated aqueous sodium bicarbonate, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonylpyridin-2-yl)-5-(trifluoromethylsulfanyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 443) 0.87 g and 2-(3-ethylsulfonylpyridin-2-yl)-5-(trifluoromethylsulfinyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 444) 0.17 g.

Present Fused Heterocyclic Compound 443

¹H-NMR (CDCl₃) δ: 9.03 (1H, dd), 8.60 (1H, dd), 8.19 (1H, d), 7.80-7.71 (3H, m), 4.02 (2H, q), 1.43 (3H, t).

Present Fused Heterocyclic Compound 444

¹H-NMR (CDCl₃) δ: 9.04 (1H, dd), 8.61 (1H, dd), 8.35 (1H, d), 7.96-7.86 (2H, m), 7.77 (1H, dd), 4.01 (2H, q), 1.44 (3H, t).

Production Example 70

To a mixture of the present fused heterocyclic compound 443 (0.35 g) and chloroform 8 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.43 g, and then the mixture was stirred at 40° C. for 6 hr. The reaction mixture was allowed to cool to RT, and to the mixture was added aqueous 10% sodium sulfite, and the reaction mixture was extracted with chloroform. The organic layer was washed with saturated aqueous sodium bicarbonate, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. To the resultant residue was added acetonitrile 4 mL, sodium tungstate dihydrate 30 mg, and aqueous hydrogen peroxide (30%) 4 mL, and the mixture was stirred at 80° C. for 6 hr. The reaction mixture was allowed to cool to RT, and to the mixture was added water. The precipitated solid was removed by filtration, and to the filtrate was added aqueous 10% sodium sulfite. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonylpyridin-2-yl)-5-(trifluoromethylsulfonyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 445) 0.35 g.

Present Fused Heterocyclic Compound 445

¹H-NMR (CDCl₃) δ: 9.05 (1H, dd), 8.61 (1H, dd), 8.59 (1H, d), 8.17 (1H, dd), 7.96 (1H, d), 7.80 (1H, dd), 3.98 (2H, q), 1.45 (3H, t).

Production Example 71 (1)

A mixture of 2-amino-4-(trifluoromethylsulfanyl)phenol 1.0 g, 3-chloro-5-trifluoromethylpicolinic acid 1.08 g, EDC hydrochloride 1.10 g, and chloroform 10 mL was stirred at RT for 1 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate, water, and brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 3-chloro-5-trifluoromethyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide 1.94 g.

3-chloro-5-trifluoromethyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide

¹H-NMR (CDCl₃) δ: 8.78 (1H, d), 8.15 (1H, d), 8.09 (1H, d), 7.37 (1H, dd), 7.04 (1H, d).

Production Example 71 (2)

To a mixture of 3-chloro-5-trifluoromethyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide 1.93 g, DMF 6 mL, THF 1 mL, and ethyl mercaptan 0.38 mL at ice temperature was added potassium tert-butoxide 0.62 g, and the mixture was stirred at RT for 2 hr. To the reaction mixture was added water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 3-ethylsulfanyl-5-trifluoromethyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide 1.45 g.

3-Ethylsulfanyl-5-trifluoromethyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide

¹H-NMR (CDCl₃) δ: 10.31 (1H, s), 8.96 (1H, brs), 8.58 (1H, d), 7.91 (1H, d), 7.70 (1H, d), 7.43 (1H, dd), 7.07 (1H, d), 3.00 (2H, q), 1.47 (3H, t).

Production Example 71 (3)

A mixture of 3-ethylsulfanyl-5-trifluoromethyl-N-[2-hydroxy-5-(trifluoromethylsulfanyl)phenyl]picolinamide 1.45 g, DMEAD 1.19 g, triphenylphosphine 1.29 g, and THF 30 mL was stirred at RT for 1 hr and at 50° C. for 1 hr. The reaction mixture allowed to cool to RT was concentrated under reduced pressure, and then to the residue was added water, the resulting mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-5-(trifluoromethylsulfanyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 451) 1.31 g.

Present Fused Heterocyclic Compound 451

¹H-NMR (CDCl₃) δ: 8.78 (1H, d), 8.30 (1H, s), 7.94 (1H, d), 7.77-7.75 (2H, m), 3.11 (2H, q), 1.51 (3H, t).

Production Example 72

To a mixture of the present fused heterocyclic compound 451 (1.13 g) and chloroform 25 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.56 g, and then the mixture was stirred at 0° C. for 40 min. To the reaction mixture was added aqueous 10% sodium sulfite, and the reaction mixture was extracted with chloroform. The organic layer was washed with saturated aqueous sodium bicarbonate, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfinyl-5-trifluoromethylpyridin-2-yl)-5-(trifluoromethylsulfanyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 452) 1.01 g.

Present Fused Heterocyclic Compound 452

¹H-NMR (CDCl₃) δ: 9.13 (1H, d), 8.91 (1H, d), 8.25 (1H, s), 7.85-7.79 (2H, m), 3.60-3.49 (1H, m), 3.13-3.02 (1H, m), 1.44 (3H, t).

Production Example 73

To a mixture of the present fused heterocyclic compound 452 (1.01 g) and chloroform 20 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.56 g, and then the mixture was stirred at RT for 6 hr. To the reaction mixture was added m-chloroperbenzoic acid (65 t or more purity) 0.20 g, and then the reaction mixture was stirred at RT for 3 hr. To the reaction mixture was added aqueous 10% sodium sulfite, and the reaction mixture was extracted with chloroform. The organic layer was washed with saturated aqueous sodium bicarbonate, and dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-5-(trifluoromethylsulfanyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 453) 0.53 g and 2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-5-(trifluoromethylsulfinyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 454) 0.48 g.

Present Fused Heterocyclic Compound 453

¹H-NMR (CDCl₃) δ: 9.25 (1H, d), 8.84 (1H, d), 8.22 (1H, d), 7.82 (1H, dd), 7.77 (1H, d), 4.11 (2H, q), 1.47 (3H, t).

Present Fused Heterocyclic Compound 454

¹H-NMR (CDCl₃) δ: 9.27 (1H, d), 8.85 (1H, d), 8.39 (1H, s), 7.96 (1H, d), 7.92 (1H, d), 4.09 (2H, q), 1.48 (3H, t).

Production Example 74

The present fused heterocyclic compound 454 (0.26 g), acetonitrile 4 mL, sodium tungstate dihydrate 18 mg, and aqueous hydrogen peroxide (30%) 3.5 mL was mixed, and the mixture was stirred at 85° C. for 5 hr. The reaction mixture was allowed to cool to RT, and to the mixture was added aqueous hydrogen peroxide (30%) 0.5 mL, and the mixture was stirred at 85° C. for 3 hr. The reaction mixture was allowed to cool to RT, and to the mixture was added water. The precipitated solid was removed by filtration, and to the filtrate was added aqueous 10% sodium sulfite. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-5-(trifluoromethylsulfonyl)benzoxazole (hereinafter referred to as the present fused heterocyclic compound 455) 0.24 g.

Present Fused Heterocyclic Compound 455

¹H-NMR (CDCl₃) δ: 9.28 (1H, d), 8.84 (1H, d), 8.62 (1H, d), 8.21 (1H, dd), 8.00 (1H, d), 4.05 (2H, q), 1.49 (3H, t).

Production Example 75 (1)

A mixture of tert-butanol 27 mL and potassium hydroxide 3.15 g was stirred with heating to reflux for 1 hr. To the mixture was added 2-chloro-5-trifluoromethylsulfanylpyridine 6.0 g and tert-butanol 3 mL with dropping funnel, and the mixture was stirred with heating to reflux for 5 hr. The reaction mixture was allowed to cool to RT, and to the mixture was added concentrated hydrochloric acid. The solid was filtered and washed with ethanol. The resulting filtrate was concentrated under reduced pressure. To the residue was added 1 N hydrochloric acid. The precipitated solid was collected by filtration and washed with water, and then with hexane, and dried to give 2-hydroxy-5-trifluoromethylsulfanylpyridine 4.42 g.

2-Hydroxy-5-trifluoromethylsulfanylpyridine

¹H-NMR (CDCl₃) δ: 7.73 (1H, d), 7.62 (1H, dd), 6.61 (1H, d).

Production Example 75 (2)

To a mixture of 2-hydroxy-5-trifluoromethylsulfanylpyridine 2 g and concentrated sulfuric acid 10 mL at ice temperature was added fuming nitric acid 0.74 mL, and the mixture was stirred at 60° C. for 2 hr. The reaction mixture was allowed to cool to RT, and then to ice water 50 mL was poured the mixture, and then the resulting mixture was extracted with ethyl acetate. The organic layer was washed with brine, and dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting solid was washed with tert-butyl methyl ether to give 2-hydroxy-3-nitro-5-trifluoromethylsulfinylpyridine 2.13 q.

2-Hydroxy-3-nitro-5-trifluoromethylsulfinylpyridine

¹H-NMR (DMSO-D₆) δ: 8.67 (1H, bra), 8.59 (1H, bra).

Production Example 75 (3)

A mixture of iron powder 4.6 g, acetic acid 0.5 mL, ethanol 20 mL, and water 15 mL was stirred at 70° C. To the mixture was added 2-hydroxy-3-nitro-5-trifluoromethylsulfinylpyridine 2 g, and the mixture was stirred at 70° C. for 2 hr. The reaction mixture was allowed to cool to RT and filtrated through Celite (Trademark). The filtrates were concentrated under reduced pressure, and to the resultant residue was added saturated aqueous sodium bicarbonate. The resulting mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting solid was washed with tert-butyl methyl ether to give 3-amino-2-hydroxy-5-trifluoromethylsulfinylpyridine 1.45 g.

3-Amino-2-hydroxy-5-trifluoromethylsulfinylpyridine

¹H-NMR (DMSO-Ds) δ: 12.23 (1H, brs), 7.49 (1H, s), 6.68 (1H, 5), 5.72 (2H, brs).

Production Example 75 (4)

A mixture of 3-amino-2-hydroxy-5-trifluoromethylsulfinylpyridine 0.63 g, 3-ethylsulfanylpicolinic acid 0.55 g, EDC hydrochloride 0.68 g and pyridine 20 ml was stirred at RT 3 hr. To the reaction mixture was added water, the mixture was stirred at RT for 30 min. The precipitated solids were collected by filtration, and concentrated under reduced pressure to give 3-ethylsulfanyl-N-[2-hydroxy-5-trifluoromethylaulfinylpyridin-3-yl]picolinamide 0.73 g.

3-Ethylsulfanyl-N-[2-hydroxy-5-trifluoromethylsulfinylpyridin-3-yl]picolinamide

¹H-NMR (DMSO-D₆) δ: 10.83 (1H, s), 8.71 (1H, s), 8.48 (1H, dd), 8.09 (1H, d), 7.98 (1H, d), 7.65 (1H, dd), 2.99 (2H, q), 1.31 (3H, t).

Production Example 75 (5)

A mixture of 3-ethylsulfanyl-N-[2-hydroxy-5-trifluoromethylsulfinylpyridin-3-yl]picolinamide 0.67 g, DMEAD 0.64 g, triphenylphosphine 0.68 g, and THF 40 mL was stirred at 50° C. for 3 hr. The reaction mixture allowed to cool to RT was concentrated under reduced pressure, and to the mixture was added water, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous ammonium chloride and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resultant residue is treated with silica gel column chromatography to give 2-(3-ethylsulfanylpyridin-2-yl)-6-(trifluoromethylsulfinyl)oxazolo[5,4-b]pyridine 0.59 g (hereinafter referred to as the present fused heterocyclic compound 474).

Present Fused Heterocyclic Compound 474

¹H-NMR (CDCl³) δ: 8.76 (1H, d), 8.70 (1H, d), 8.64 (1H, dd), 7.82 (1H, dd), 7.47 (1H, dd), 3.09 (2H, q), 1.47 (3H, t).

Production Example 76

To a mixture of the present fused heterocyclic compound 474 (0.43 g) and chloroform 30 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.53 g, and then the mixture was stirred at RT for 5 hr. To the reaction mixture was added aqueous 10% sodium sulfite, and the mixture was extracted with chloroform. The organic layer was washed with saturated aqueous sodium bicarbonate, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonylpyridin-2-yl)-6-(trifluoromethylsulfinyl)oxazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 439) 0.34 g.

Present Fused Heterocyclic Compound 439

¹H-NMR (CDCl₃) δ: 9.08 (1H, dd), 8.80 (1H, d), 8.69 (1H, d), 8.60 (1H, dd), 7.81 (1H, dd), 3.91 (2H, q), 1.45 (3H, t).

Production Example 77

The present fused heterocyclic compound 439 (0.17 g), acetonitrile 4 mL, sodium tungstate dihydrate 14 mg, and aqueous hydrogen peroxide (30%) 4 mL was mixed, and the mixture was stirred at 80° C. for 4 hr. To the reaction mixture allowed to cool to RT was added water, and the precipitated solid was collected by filtration, and the solids and aqueous 10% sodium sulfite were mixed, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resultant residue is treated with silica gel column chromatography to give 2-(3-ethylsulfonylpyridin-2-yl)-6-(trifluoromethylsulfonyl) oxazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 440) 0.09 g.

Present Fused Heterocyclic Compound 440

¹H-NMR (CDCl₃) δ: 9.13 (1H, dd), 9.09 (1H, dd), 8.79 (1H, d), 8.60 (1H, dd), 7.83 (1H, dd), 3.88 (2H, q), 1.46 (3H, t).

Production Example 78 (1)

A mixture of 3-amino-2-hydroxy-5-trifluoromethylsulfinylpyridine 0.67 g, 3-ethylsulfanyl-5-trifluoromethylpicolinic acid 0.75 g, EDC hydrochloride 0.68 g and pyridine 20 mL was stirred at RT for 1.5 hr. To the reaction mixture was added water, and the mixture was stirred at RT for 30 min. The precipitated solids were collected by filtration and dried under reduced pressure to give 3-ethylsulfanyl-5-trifluoromethyl-N-[2-hydroxy-5-trifluoromethylsulfinylpyridin-3-yl]picolinamide.

3-Ethylsulfanyl-5-trifluoromethyl-N-[2-hydroxy-5-trifluoromethylsulfinylpyridin-3-yl]picolinamide 1.28 g

¹H-NMR (CDCl₃) δ: 10.99 (1H, dd), 8.90 (1H, s), 8.68 (18, a), 7.91 (1H, s), 7.81 (1H, s), 3.02 (2H, q), 1.48 (3H, t).

Production Example 78 (2)

A mixture of 3-ethylsulfanyl-5-trifluoromethyl-N-[2-hydroxy-5-trifluoromethylsulfinylpyridin-3-yl]picolinamide (1.24 g), DMEAD 1.01 g, triphenylphosphine 1.06 g, and THF 40 mL was stirred at 50° C. for 3 hr. The reaction mixture allowed to cool to RT was concentrated under reduced pressure, and to the mixture is added water, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous ammonium chloride and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfanyl-5-trifluoromethylpyridin-2-yl)-6-(trifluoromethylsulfinyl) oxazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 478) 0.94 g.

Present Fused Heterocyclic Compound 478

¹H-NMR (CDCl₃) δ: 8.83 (1H, d), 8.81 (1H, d), 8.75 (1H, d), 7.97 (1H, d), 3.13 (2H, q), 1.51 (3H, t).

Production Example 79

To a mixture of the present fused heterocyclic compound 478 (0.74 g) and chloroform 30 mL at ice temperature was added m-chloroperbenzoic acid (65% or more purity) 0.77 g, and then the mixture was stirred at RT 4 hr. To the reaction mixture was added aqueous 10% sodium sulfite, and the mixture was extracted with chloroform. The organic layer was washed with saturated aqueous sodium bicarbonate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-6-(trifluoromethylsulfinyl) oxazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 449) 0.75 g.

Present Fused Heterocyclic Compound 449

¹H-NMR (CDCl₃) δ: 9.31 (1H, d), 8.84-8.81 (28, m), 8.73 (1H, d), 3.98 (2H, q), 1.49 (3H, t).

Production Example 80

The present fused heterocyclic compound 449 (0.14 g), acetonitrile 4 mL, sodium tungstate dihydrate 27 mg, and aqueous hydrogen peroxide (30%) 4 mL were mixed, and the mixture was stirred at 80° C. for 5 hr. To the reaction mixture allowed to cool to RT was added water, and the precipitated solids were collected by filtration. The solids and aqueous 10% sodium sulfite were mixed and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resultant residue was treated with silica gel column chromatography to give 2-(3-ethylsulfonyl-5-trifluoromethylpyridin-2-yl)-6-(trifluoromethylsulfonyl)oxazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 450) 0.21 g.

Present Fused Heterocyclic Compound 450

¹H-NMR (CDCl₃) δ: 9.32 (1H, d), 9.17 (1H, d), 8.85-8.82 (2H, m), 3.95 (2H, q), 1.50 (3H, t).

Production Example 81

To a mixture of the present fused heterocyclic compound 440 (1 mmol) and chloroform 10 mL at ice temperature is added m-chloroperbenzoic acid (65% or more purity) 5 mmol, and then the mixture is stirred with heating to reflux for 6 hr. To the reaction mixture allowed to cool to RT is added m-chloroperbenzoic acid (65% or more purity) 5 mmol, and then the mixture is stirred with heating to reflux for 6 hr. To the reaction mixture allowed to cool to RT is added aqueous 10% sodium sulfite, and the mixture is extracted with chloroform. The organic layer is washed with saturated aqueous sodium bicarbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resultant residue is treated with silica gel column chromatography to give 2-(3-ethylsulfonylpyridin-2-yl)-6-(trifluoromethylsulfonyl)oxazolo[5,4-b]pyridine 4-oxide (hereinafter referred to as the present fused heterocyclic compound 456) and 2-(3-ethylsulfonyl-1-oxy-pyridin-2-yl)-6-(trifluoromethylsulfonyl)oxazolo[5,4-b]pyridine (hereinafter referred to as the present fused heterocyclic compound 458).

Present Fused Heterocyclic Compound 456

Present Fused Heterocyclic Compound 458

Compounds as described in the above Production example, and compounds which are prepared in a similar manner as described for the preparation of the above Production examples are listed in the following tables.

Examples of the combinations of R¹, R², R³, R⁴, R⁵, R⁶, A¹, A², and n in the compound represented by the formula (1):

are shown below in [Table 1] to [Table 20].

TABLE 1 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n  1 Et H H H CF₃ H NMe N 0  2 Et H H H CF₃ H NMe N 1  3 Et H H H CF₃ H NMe N 2  4 Et H CF₃ H CF₃ H NMe N 0  5 Et H CF₃ H CF₃ H NMe N 2  6 Et H H H CF₂CF₃ H NMe N 0  7 Et H H H CF₂CF₃ H NMe N 1  8 Et H H H CF₂CF₃ H NMe N 2  9 Et H H H I H NMe N 0 10 Et H CF₃ H CF₃ H S N 0 11 Et H CF₃ H CF₃ H S N 2 12 Et H H H CF₃ H S N 2 13 Et H H H SCF₃ H NMe N 0 14 Et H H H SCF₃ H NMe N 1 15 Et H H H SCF₃ H NMe N 2 16 Et H H H SO₂CF₃ H NMe N 2 17 Et H CF₃ H CF₂CF₃ H NMe N 0 18 Et H CF₃ H CF₂CF₃ H NMe N 1 19 Et H CF₃ H CF₂CF₃ H NMe N 2 20 Et H H H SOCF₃ H NMe N 2 21 Et H H H I H NMe CH 0  22* Et H H H CF₃ H S N 2 23 Et H H H SF₅ H NMe CH 0 24 Et H H H SF₅ H NMe CH 2 25 Et H CF₃ H SO₂CF₃ H NMe N 2

TABLE 2 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 26 Et H H H CF₂CF₃ H NMe CH 0 27 Et H H H CF₂CF₃ H NMe CH 2 28 Et H CF₃ H SCF₃ H NMe N 0 29 Et H CF₃ H SCF₃ H NMe N 1 30 Et H H H CF₃ H NMe CH 0 31 Et H H H CF₃ H NMe CH 1 32 Et H H H CF₃ H NMe CH 2 33 Et H CF₃ H CF₃ H NMe CH 0 34 Et H CF₃ H CF₃ H NMe CH 1 35 Et H CF₃ H CF₃ H NMe CH 2  36* Et H H H CF₃ H NMe N 2  37* Et H H H CF₃ H NMe N 2 38 Et H CF₃ H CF₂CF₃ H NMe CH 0 39 Et H CF₃ H CF₂CF₃ H NMe CH 1 40 Et H CF₃ H CF₂CF₃ H NMe CH 2 41 Et H H H CF3 H S N 0 42 Et H CF₃ H I H NMe N 0 43 Et H CF₃ H SH H NMe N 0 44 Et H CF₃ H SCF₃ H NMe N 2 45 Et H CF₃ H I H NMe CH 0 46 Et H H H CF₃ H NMe CBr 2  47* Et H H H CF₂CF₃ H NMe CH 2  48* Et H CF₃ H CF₃ H NMe N 2 49 Et H H H OCF₃ H NMe CH 0 50 Et H H H OCF₃ H NMe CH 2

TABLE 3 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n  51* Et H CF₃ H CF₃ H NMe N 2 52 Et H H H CF₃ H S CH 0 53 Et H H H CF₃ H S CH 2 54 Et H CF₃ H CF₃ H S CH 0 55 Et H CF₃ H CF₃ H S CH 2 56 Et H H H CF₃ OMe NMe CH 2 57 Et H H H C(OH)₂CF₃ H NMe N 0 58 Et H H H C(OH)₂CF₃ H NMe N 2 59 Et H CF₃ H CO₂Me H NMe N 0 60 Et H CF₃ H SOCF₃ H NMe N 2 61 Et H H H SCF₃ H NMe CH 0 62 Et H H H SCF₃ H NMe CH 1 63 Et H H H SCF₃ H NMe CH 2 64 Et H H H SO₂CF₃ H NMe CH 2 65 Et H H H CF₃ H NCH₂CF₃ N 0 66 Et H CF₃ H CF₃ H NCH₂CF₃ N 0 67 Et H H H CF₃ H NCH₂CF₃ N 2 68 Et H CF₃ H CF₃ H NCH₂CF₃ N 2 69 Et H CF₃ H CO₂Me H NMe N 2  70* Et H CF₃ H CO₂Me H NMe N 2 71 Et H CF₂CF₃ H CF₃ H NMe N 0 72 Et H CF₂CF₃ H CF₃ H NMe N 2 73 Et H CF₂CF₃ H CF₂CF₃ H NMe N 0 74 Et H CF₂CF₃ H CF₂CF₃ H NMe N 2 75 Et H H H CF₃ H NMe CBr 0

TABLE 4 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 76 Et H H H CF₃ H NH N 0 77 Et H H H CF₃ H NH N 2 78 Et H CF₃ H CF₃ H NH N 0 79 Et H CF₃ H CF₃ H NH N 2 80 Et H H H CF₃ H O N 0 81 Et H H H CF₃ H O N 2 82 Et H CF₃ H CF₃ H O N 0 83 Et H CF₃ H CF₃ H O N 2 84 Et H H H CF₃ H O CH 0 85 Et H H H CF₃ H O CH 2 86 Et H CF₃ H CF₃ H O CH 0 87 Et H CF₃ H CF₃ H O CH 2 88 Et H H H CF₃ Cl NMe N 2 89 Et H CF₃ H CF₃ Cl NMe N 2 90 Et H H H CF₃ OC(O)Me NMe N 2 91 Et H CF₃ H CF₃ OC(O)Me NMe N 2 92 Et H H H CF₃ OH NMe N 2 93 Et H CF₃ H CF₃ OH NMe N 2 94 Et H H H CF₃ OMe NMe N 2 95 Et H CF₃ H CF₃ OMe NMe N 2 96 Et H H H CF₃ SMe NMe N 2 97 Et H CF₃ H CF₃ SMe NMe N 2 98 Et H H H CF₃ NMe₂ NMe N 2 99 Et H CF₃ H CF₃ NMe₂ NMe N 2 100 CH₂CycPr H H H CF₃ H NMe N 2

TABLE 5 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 101 CH₂CycPr H CF₃ H CF₃ H NMe N 2 102 CF₃ H H H CF₃ H NMe N 2 103 CF₃ H CF₃ H CF₃ H NMe N 2 104 CH₂CF₃ H H H CF₃ H NMe N 2 105 CH₂CF₃ H CF₃ H CF₃ H NMe N 2 106 Et Cl H H CF₃ H NMe N 2 107 Et H Cl H CF₃ H NMe N 2 108 Et H H Cl CF₃ H NMe N 2 109 Et H OCF₃ H CF₃ H NMe N 2 110 Et H SCF₃ H CF₃ H NMe N 2 111 Et H SOCF₃ H CF₃ H NMe N 2 112 Et H SO₂CF₃ H CF₃ H NMe N 2 113 Et H CF(CF₃)₂CF₃ H CF₃ H NMe N 2 114 Et H CF₂CF₂CF₃ H CF₃ H NMe N 2 115 Et H Br H CF₃ H NMe N 2 116 Et H I H CF₃ H NMe N 2 117 Et H Me H CF₃ H NMe N 2 118 Et H OMe H CF₃ H NMe N 2 119 Et H H H CF(CF₃)₂ H NMe N 2 120 Et H CF₃ H CF(CF₃)₂ H NMe N 2 121 Et H CF₃ H SF₅ H NMe N 2 122 Et H H H CF₂CF₂CF₃ H NMe N 2 123 Et H CF₃ H CF₂CF₂CF₃ H NMe N 2 124 Et H H H SCF₂CF₃ H NMe N 2 125 Et H CF₃ H SCF₂CF₃ H NMe N 2

TABLE 6 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 126 Et H H H SO₂CF₂CF₃ H NMe N 2 127 Et H CF₃ H SO₂CF₂CF₃ H NMe N 2 128 Et H H H CF₃ H NCH₂OMe N 2 129 Et H CF₃ H CF₃ H NCH₂OMe N 2 130 Et H H H CF₃ H NMe CCN 2 131 Et H CF₃ H CF₃ H NMe CCN 2 132 Et H H H CF₃ H NMe CF 2 133 Et H CF₃ H CF₃ H NMe CF 2 134 Et H H H CF₃ H NMe CMe 2 135 Et H CF₃ H CF₃ H NMe CMe 2 136 Et H H H CF₃ H NMe COMe 2 137 Et H CF₃ H CF₃ H NMe COMe 2 138 Et H H H CF₃ H NMe CSCH₂CH₃ 2 139 Et H CF₃ H CF₃ H NMe CSCH₂CH₃ 2 140 Et H H H CF₃ H NMe CSO₂CH₂CH₃ 2 141 Et H CF₃ H CF₃ H NMe CSO₂CH₂CH₃ 2 142 Me H H H CF₃ H NMe N 0 143 Me H H H CF₃ H NMe N 1 144 Me H H H CF₃ H NMe N 2 145 Pr H H H CF₃ H NMe N 0 146 Pr H H H CF₃ H NMe N 1 147 Pr H H H CF₃ H NMe N 2 148 iPr H H H CF₃ H NMe N 0 149 iPr H H H CF₃ H NMe N 1 150 iPr H H H CF₃ H NMe N 2

TABLE 7 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 151 tBu H H H CF₃ H NMe N 0 152 tBu H H H CF₃ H NMe N 1 153 tBu H H H CF₃ H NMe N 2 154 CF₃ H H H CF₃ H NMe N 0 155 CF₃ H H H CF₃ H NMe N 1 156 Et H H H CF₃ H NEt N 0 157 Et H H H CF₃ H NEt N 1 158 Et H H H CF₃ H NEt N 2 159 Et H H H CF₃ H NPr N 0 160 Et H H H CF₃ H NPr N 1 161 Et H H H CF₃ H NPr N 2 162 Et H H H CF₃ H NiPr N 0 163 Et H H H CF₃ H NiPr N 1 164 Et H H H CF₃ H NiPr N 2 165 Et H H H CF₃ H NCycPr N 0 166 Et H H H CF₃ H NCycPr N 1 167 Et H H H CF₃ H NCycPr N 2 168 Et H H H CF₃ H NCH₂OEt N 0 169 Et H H H CF₃ H NCH₂OEt N 1 170 Et H H H CF₃ H NCH₂OEt N 2 171 Et H H H CF₃ H NCH₂OMe N 0 172 Et H H H Me H NMe N 0 173 Et H H H Me H NMe N 1 174 Et H H H Me H NMe N 2 175 Et H H H Br H NMe N 0

TABLE 8 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 176 Et H H H Br H NMe N 1 177 Et H H H Br H NMe N 2 178 Et H H H I H NMe N 1 179 Et H H H I H NMe N 2 180 Et H H H CN H NMe N 0 181 Et H H H CN H NMe N 1 182 Et H H H CN H NMe N 2 183 Et H H H CHO H NMe N 0 184 Et H H H CF₂H H NMe N 0 185 Et H H H CF₂H H NMe N 1 186 Et H H H CF₂H H NMe N 2 187 Me H H H CF₃ H NMe CH 0 188 Et H H H CF₃ H NMe CCl 0 189 Et H H H CF₃ H NMe CCl 1 190 Et H H H CF₃ H NMe CCl 2 191 Et H H H CF₃ H NMe CBr 1 192 Me H H H CF₃ H O CH 0 193 Et H H H CF₃ H O CH 1 194 Et H H H CF₃ H O N 1 195 Me H H H CF₃ H S CH 0 196 Et H H H CF₃ H S CH 1 197 Et Cl H H CF₃ H NMe N 0 198 Et Cl H H CF₃ H NMe N 1 199 Et H H H COCF₃ H NMe N 0 200 Et H H H Cl H NMe N 0

TABLE 9 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 201 Et H H H Cl H NMe N 1 202 Et H H H Cl H NMe N 2 203 Et H H H Br H NMe N 0 204 Et H H SEt CF₃ H NMe N 0 205 Et H H H CF₃ H NCH₂OEt CH 0 206 Et H H H CF₃ H NCH₂CO₂Me N 0 207 Et H H H CF₃ H NCH₂CO₂Et N 0 208 Et H H H CF₃ H N(CH₂)₂OMe N 0 209 Et H H H CF₃ H NBu N 0 210 Et H H H CF₃ H NCO₂tBu N 0 211 Et H H H CH(OH)CF₃ H NMe N 0 212 Et H H H CHFCF₃ H NMe N 0 213 Et H F H CF₃ H NMe N 0 214 Et H F H CF₃ H NMe N 1 215 Et H F H CF₃ H NMe N 2 216 Et OMe H H CF₃ H NMe N 0 217 Et OMe H H CF₃ H NMe N 1 218 Et H OMe H CF₃ H NMe N 0 219 Et H OMe H CF₃ H NMe N 1 220 Et H OH H CF₃ H NMe N 0 221 Et H H H NH₂ H NMe N 0 222 Et H H H CHFCF₃ H NMe N 1 223 Et H H H CHFCF₃ H NMe N 2 224 Et H H H CF₂CF₂CF₃ H NMe N 0 225 Et H H H CF₂CF₂CF₃ H NMe N 1

TABLE 10 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 226 Et Cl H H CF₂CF₃ H NMe N 1 227 Et Cl H H CF₂CF₃ H NMe N 2 228 Et H Cl H CF₃ H NMe N 0 229 Et H Cl H CF₃ H NMe N 1 230 Et H Cl H CF₂CF₃ H NMe N 1 231 Et H H Cl CF₃ H NMe N 0 232 Et H H Cl CF₃ H NMe N 1 233 Et H H OMe CF₃ H NMe N 0 234 Et H H OMe CF₃ H NMe N 1 235 Et H H OMe CF₃ H NMe N 2 236 Et H H H SH H NMe N 0 237 Et H H H Et H NMe N 0 238 Et H H H iPr H NMe N 0 239 Et H H H NHEt H NMe N 0 240 Et H H H NEt₂ H NMe N 0 241 Et H H H tBu H NMe N 0 242 Et H H H H CF₃ NMe N 0 243 Et F H H CF₃ H NMe N 0 244 Et F H H CF₃ H NMe N 1 245 Et F H H CF₃ H NMe N 2 246 Et H H H H CF₃ NMe N 1 247 Et H H H H CF₃ NMe N 2 248 Et H H H NMe₂ H NMe N 0 249 Et H H H NHCOMe H NMe N 0 250 Et H H H CH₂CF₃ H NMe N 0

TABLE 11 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 251 Et H H H NMeCOMe H NMe N 0 252 Et H H H NH2 H NMe N 1 253 Et H CF₃ H CF₃ H NMe N 1 254 Et H H H NHCOCF₃ H NMe N 0 255 Et H H H NHCOCF₃ H NMe N 1 256 Et H H H NHCOCF₃ H NMe N 2 257 Et H H H CF₃ H S N 1 258 CH₂CF₃ H H H CF₃ H NMe N 0 259 CH₂CF₃ H H H CF₃ H NMe N 1 260 Et Me H H CF₃ H NMe N 0 261 Et Me H H CF₃ H NMe N 1 262 Et Me H H CF₃ H NMe N 2 263 Et H Me H CF₃ H NMe N 0 264 Et H Me H CF₃ H NMe N 1 265 Et H H CF₃ CF₃ H NMe N 0 266 Et H H CF₃ CF₃ H NMe N 1 267 Et H H CF₃ CF₃ H NMe N 2 268 Et H Br H CF₃ H NMe N 0 269 Et H Br H CF₃ H NMe N 1 270 Et H CN H CF₃ H NMe N 0 271 Et H CN H CF₃ H NMe N 1 272 Et H CN H CF₃ H NMe N 2 273 Et H CF₂CF₃ H CF₃ H NMe N 1 274 Et H CHO H CF₃ H NMe N 0 275 Et H H H SMe H NMe N 0

TABLE 12 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 276 Et H H H SO₂Me H NMe N 2 277 Et H H H SEt H NMe N 0 278 Et H H H SO₂Et H NMe N 2 279 Et H H H SO₂iPr H NMe N 2 280 Et H H H SCH₂CF₃ H NMe N 0 281 Et H H H SO₂CH₂CF₃ H NMe N 2 282 Et H H H SCF₂CF₃ H NMe N 0 283 Et H H H SCF₂CF₂CF₃ H NMe N 0 284 Et H H H SCF(CF₃)₂ H NMe N 0 285 Et H H H CH(OH)CF₃ H NMe N 0 286 Et H H H CH(Cl)CF₃ H NMe N 0 287 Et H H H OH H NMe N 0 288 Et H H H OH H NMe N 2 289 Et H H H OCF₂Br H NMe N 2 290 Et H H H OCF₃ H NMe N 2 291 Et H H H SCF₂CF₃ H NMe N 1 292 Et H H H SCF₂CF₂CF₃ H NMe N 1 293 Et H H H SCF₂CF₂CF₃ H NMe N 2 294 Et H H H StBu H NMe N 0 295 Et H H H SO₂tBu H NMe N 2 296 Et H CF₃ H Br H NMe N 0 297 Et H CF₃ H Br H NMe N 1 298 Et H CF₃ H Br H NMe N 2 299 Et H I H CF₂CF₃ H NMe N 2 300 Et H NO₂ H CF₃ H NMe N 0

TABLE 13 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 301 Et H NO₂ H CF₃ H NMe N 1 302 Et H NO₂ H CF₃ H NMe N 2 303 Et H I H SCF₃ H NMe N 2 304 Et H I H SO₂CF₃ H NMe N 2 305 Et H Br H CF₂CF₃ H NMe N 2 306 Et H Cl H CF₃ H S N 0 307 Et H Cl H CF₃ H S N 2 308 Et H H H C(OH)(CF₃)₂ H NMe N 0 309 Et H H H C(Cl)(CF₃)₂ H NMe N 0 310 Et H H H C(Cl)(CF₃)₂ H NMe N 1 311 Et H H H C(Cl)(CF₃)₂ H NMe N 2 312 Et H Cl H CF₂CF₃ H NMe N 2 313 Et H H H H CF(CF₃)₂ NMe CH 0 314 Et H H H CF(CF₃)₂ H NMe CH 0 315 Et H CF₃ H I H NMe N 2 316 Et H H H CF₂CF₃ H NMe CH 1 317 Et H H H SF₅ H NMe CH 1 318 Et H CF₃ H SF₅ H NMe CH 0 319 Et H CF₃ H SF₅ H NMe CH 1 320 Et H Me H CF₂CF₃ H NMe N 0 321 Et H Me H CF₂CF₃ H NMe N 1 322 Et H Me H CF₂CF₃ H NMe N 2 323 Et H H H I H S N 0 324 Et H CF₃ H I H S N 0 325 Et H H H CF₂CF₃ H S N 0

TABLE 14 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 326 Et H CF₃ H CF₂CF₃ H S N 0 327 Et H H H CF₂CF₃ H S N 2 328 Et H CF₃ H CF₂CF₃ H S N 2 329 Et H Et H CF₃ H NMe N 2 330 Et H H H SO₂NMe₂ H NMe N 1 331 Et H H H SO₂NMe₂ H NMe N 2 332 Et H H H CF₃ H NMe CNH₂ 0 333 Et H Br H SCF₃ H NMe N 2 334 Et H H H CF₃ H NMe CNMe₂ 0 335 Et H CF₃ H CF₃ H NMe CNH₂ 0 336 Et H CF₃ H CF₃ H NMe CNMe₂ 0 337 Et H SF₅ H CF₃ H NMe N 0 338 Et H SF₅ H CF₃ H NMe N 1 339 Et H SF₅ H CF₃ H NMe N 2 340 Et H H H CF(CF₃)₂ H NH CH 0 341 Et H H H Br H NMe N 0 342 Et H H H Br H NMe N 1 343 Et H H H Br H NMe N 2 344 Et H H H Br H NMe N 0 345 Et H H H CF₃ H NH N 1 346 Et H H H CF₃ H NH CH 0 347 Et H CF₃ H CF₃ H NEt N 2 348 Et H CF₃ H CF₃ H NCH₂CN N 2 349 Et H CF₃ H CF₃ H NCH₂OEt N 2 350 Et H CF₃ H CF₃ H NPr N 2

TABLE 15 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 351 Et H CF₃ H CF₃ H N(CH₂)₃CH₃ N 2 352 Et H CF₃ H CF₃ H NCH₂CO₂Me N 2 353 Et H CF₃ H CF₃ H NCO₂tBu N 2 354 Et H CF₃ H CF₃ H NCO₂Me N 2 355 Et H CF₃ H CF₃ H NCOMe N 2 356 Et H OCF₃ H CF₃ H NMe N 0 357 Et H OCF₃ H CF₃ H NMe N 1 358 Et H CF₂CF₂CF₂CF₃ H CF₃ H NMe N 2 359 Et H NH₂ H CF₃ H NMe N 2 360 Et H NHCOCF₃ H CF₃ H NMe N 2 361 Et H iPr H CF₃ H NMe N 2 362 Et H CHO H CF₃ H NMe N 2 363 Bu H H H CF₃ H NMe N 0 364 CH₂CN H H H CF₃ H NMe N 0 365 CH₂tBu H H H CF₃ H NMe N 0 366 CH₂CH₂CN H H H CF₃ H NMe N 0 367 CH₂CycBu H H H CF₃ H NMe N 0 368 CF₂Br H H H CF₃ H NMe N 0 369 Et H CF₂H H CF₃ H NMe N 2 370 Et H CH₂OH H CF₃ H NMe N 2 371 Bu H H H CF₃ H NMe N 2 372 CH₂CN H H H CF₃ H NMe N 2 373 CH₂tBu H H H CF₃ H NMe N 2 374 CH₂CH₂CN H H H CF₃ H NMe N 2 375 CH₂CycBu H H H CF₃ H NMe N 2

TABLE 16 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 376 CF₂Br H H H CF₃ H NMe N 2 377 Et H CH₂F H CF₃ H NMe N 2 378 Et H H H H CF₃ S N 0 379 Et H H H H CF₃ S N 2 380 Et H OCF₃ H CF₂CF₃ H NMe N 0 381 Et H OCF₃ H CF₂CF₃ H NMe N 1 382 Et H OCF₃ H CF₂CF₃ H NMe N 2 383 Et H CF₃ H CF₃ H NMe CMe 0 384 Et H CF₃ H CF₃ H NMe CMe 1 385 Et H CF₃ H CF₃ H NMe CF 0 386 Et H CF₃ H CF₃ H NMe CF 1 387 CH₂CycPr H H H CF₃ H NMe N 0 388 CH₂CycPr H H H CF₃ H NMe N 1 389 Et H CF₃ H CF₃ H NMe CBr 0 390 Et H CF₃ H CF₃ H NMe CSCH₂CH₃ 0 391 Et H OCF₃ H SCF₃ H NMe N 0 392 Et H OCF₃ H SCF₃ H NMe N 1 393 Et H OCF₃ H SCF₃ H NMe N 2 394 Et H CF₃ H CF₃ H NMe CBr 1 395 Et H CF₃ H CF₃ H NMe CBr 2 396 Et H H H COMe H NMe N 0 397 Et H H H COMe H NMe N 2 398 Et H H H CF₃ CN NMe N 2 399 Et H CF₃ H CF₃ CN NMe N 2  400* Et H H H CF₃ H NMe N 2

TABLE 17 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n  401* Et H CF₃ H CF₃ H NMe N 2 402 Et H H H CF₃ H NMe COMe 0 403 Et H H H CF₃ H NMe CSCH₃ 0 404 Et H H H CF₃ H NMe CSO₂CH₃ 2 405 Et H H H CF₃ H NMe CSO₂CH₂CF₃ 2 406 Et H H H CF₃ H NMe CCN 0 407 Et H CF₃ H CF₃ COOH NMe N 2 408 Et H CF₃ H CF₃ CONH₂ NMe N 2  409* Et H CF₃ H CF₂CF₃ H NMe N 2  410* Et H CF₃ H CF₂CF₃ H NMe N 2 411 Et H CF₃ H COOH H NMe N 0 412 Et H H H CF₃ H NMe CCN 1 413 Et H H H CF₃ H NH CCF₃ 0 414 Et H C(OCH₃)₃ H CF₂CF₃ H NMe N 2 415 Et H H H H CF₃ NMe CH 0 416 Et H H H H CF₃ NMe CH 2 417 Et H H H CF₃ H NMe CCF₃ 2 418 Me H CF₃ H CF₂CF₃ H NMe N 0 419 Me H CF₃ H CF₂CF₃ H NMe N 2 420 Pr H CF₃ H CF₂CF₃ H NMe N 0 421 Pr H CF₃ H CF₂CF₃ H NMe N 2 422 iPr H CF₃ H CF₂CF₃ H NMe N 0 423 iPr H CF₃ H CF₂CF₃ H NMe N 2 424 Bu H CF₃ H CF₂CF₃ H NMe N 0 425 Bu H CF₃ H CF₂CF₃ H NMe N 2

TABLE 18 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 426 CH(CH₃)CH₂CH₃ H CF₃ H CF₂CF₃ H NMe N 0 427 CH(CH₃)CH₂CH₃ H CF₃ H CF₂CF₃ H NMe N 2 428 CH₂CH(CH₃)₂ H CF₃ H CF₂CF₃ H NMe N 0 429 CH₂CH(CH₃)₂ H CF₃ H CF₂CF₃ H NMe N 2 430 tBu H CF₃ H CF₂CF₃ H NMe N 0 431 tBu H CF₃ H CF₂CF₃ H NMe N 2 432 CH₂CF₃ H CF₃ H CF₂CF₃ H NMe N 0 433 CH₂CF₃ H CF₃ H CF₂CF₃ H NMe N 2 434 Et H CF₃ H CN H NMe N 0 435 Et H H H CF₃ H NMe CCF₃ 0 436 Et H H H SCF₃ H O N 0 437 Et H H H SCF₃ H O N 1 438 Et H H H SCF₃ H O N 2 439 Et H H H S(O)CF₃ H O N 2 440 Et H H H S(O)₂CF₃ H O N 2 441 Et H H H SCF₃ H O CH 0 442 Et H H H SCF₃ H O CH 1 443 Et H H H SCF₃ H O CH 2 444 Et H H H S(O)CF₃ H O CH 2 445 Et H H H S(O)₂CF₃ H O CH 2 446 Et H CF₃ H SCF₃ H O N 0 447 Et H CF₃ H SCF₃ H O N 1 448 Et H CF₃ H SCF₃ H O N 2 449 Et H CF₃ H S(O)CF₃ H O N 2 450 Et H CF₃ H S(O)₂CF₃ H O N 2

TABLE 19 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 451 Et H CF₃ H SCF₃ H O CH 0 452 Et H CF₃ H SCF₃ H O CH 1 453 Et H CF₃ H SCF₃ H O CH 2 454 Et H CF₃ H S(O)CF₃ H O CH 2 455 Et H CF₃ H S(O)₂CF₃ H O CH 2  456* Et H H H S(O)₂CF₃ H O N 2  457* Et H CF₃ H S(O)₂CF₃ H O N 2  458* Et H H H S(O)₂CF₃ H O N 2  459* Et H H H S(O)₂CF₃ H O CH 2  460* Et H CF₃ H S(O)₂CF₃ H O N 2  461* Et H CF₃ H S(O)₂CF₃ H O CH 2 462 Et H H H CF₂CF₃ H O N 0 463 Et H H H CF₂CF₃ H O N 1 464 Et H H H CF₂CF₃ H O N 2 465 Et H H H CF₂CF₃ H O CH 0 466 Et H H H CF₂CF₃ H O CH 1 467 Et H H H CF₂CF₃ H O CH 2 468 Et H CF₃ H CF₂CF₃ H O N 0 469 Et H CF₃ H CF₂CF₃ H O N 1 470 Et H CF₃ H CF₂CF₃ H O N 2 471 Et H CF₃ H CF₂CF₃ H O CH 0 472 Et H CF₃ H CF₂CF₃ H O CH 1 473 Et H CF₃ H CF₂CF₃ H O CH 2 474 Et H H H S(O)CF₃ H O N 0 475 Et H H H S(O)₂CF₃ H O N 0

TABLE 20 No. R¹ R² R³ R⁴ R⁵ R⁶ A¹ A² n 476 Et H H H S(O)CF₃ H O CH 0 477 Et H H H S(O)₂CF₃ H O CH 0 478 Et H CF₃ H S(O)CF₃ H O N 0 479 Et H CF₃ H S(O)₂CF₃ H O N 0 480 Et H CF₃ H S(O)CF₃ H O CH 0 481 Et H CF₃ H S(O)₂CF₃ H O CH 0

In [Table 1] to [Table 20], the symbol “*” in the leftmost column denotes that the present fused heterocyclic compound is a N-oxide. Specifically, the following compounds are included.

Present Fused Heterocyclic Compound 22

Present Fused Heterocyclic Compound 36

Present Fused Heterocyclic Compound 37

Present Fused Heterocyclic Compound 47

Present Fused Heterocyclic Compound 48

Present Fused Heterocyclic Compound 51

Present Fused Heterocyclic Compound 70

Present Fused Heterocyclic Compound 400

Present Fused Heterocyclic Compound 401

Present Fused Heterocyclic Compound 409

Present Fused Heterocyclic Compound 410

Present Fused Heterocyclic Compound 456

Present Fused Heterocyclic Compound 457

Present Fused Heterocyclic Compound 458

Present Fused Heterocyclic Compound 459

Present Fused Heterocyclic Compound 460

Present Fused Heterocyclic Compound 461

In [Table 1] to [Table 20],

-   Me represents a methyl group; -   Et represents an ethyl group; -   Pr represents a propyl group; -   Bu represents a butyl group; -   tBu represents a tertiary butyl group; -   iPr represents an isopropyl group; -   CycPr represents a cyclo propyl group.

Formulation Examples are shown below.

Formulation Example 1

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of imidacloprid, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 2

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of clothianidin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 3

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.1 parts of thiamethoxam, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 4

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.1 parts of thiacloprid, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 5

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.1 parts of acetamiprid, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 6

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.1 parts of dinotefuran, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 7

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.1 parts of nitenpyram, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 8

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of imidacloprid, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 9

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of clothianidin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 10

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of thiamethoxam, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 11

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of thiacloprid, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 12

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of acetamiprid, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 13

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of dinotefuran, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 14

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of nitenpyram, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 15

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of imidacloprid, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 16

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of clothianidin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 17

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of thiamethoxam, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 18

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of thiacloprid, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 19

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of acetamiprid, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 20

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of dinotefuran, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 21

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of nitenpyram, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 22

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of imidacloprid, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 23

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of clothianidin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 24

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of thiamethoxam, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 25

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of thiacloprid, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 26

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of acetamiprid, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 27

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of dinotefuran, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 28

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of nitenpyram, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 29

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of acrinathrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 30

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of bifenthrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 31

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of cycloprothrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 32

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of lambda-cyhalothrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 33

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of cypermethrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 34

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of deltamethrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 35

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of etofenprox, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 36

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of fenpropathrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 37

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of fenvalerate, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 38

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of esfenvalerate, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 39

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of permethrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 40

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of silafluofen, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 41

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of tefluthrin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 42

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of acrinathrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 43

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of bifenthrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 44

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of bifenthrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 45

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of lambda-cyhalothrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 46

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of cypermethrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 47

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of deltamethrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 48

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of etofenprox, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 49

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of fenpropathrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 50

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of fenvalerate, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 51

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of esfenvalerate, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 52

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of permethrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 53

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of silafluofen, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 54

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of tefluthrin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 55

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of acrinathrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 56

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of bifenthrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 57

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of cyhalothrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 58

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of lambda-cyhalothrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 59

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of cypermethrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 60

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of deltamethrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 61

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of etofenprox, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 62

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of fenpropathrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 63

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of fenvalerate, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 64

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of esfenvalerate, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 65

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of permethrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 66

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of silafluofen, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 67

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of tefluthrin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 68

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of acrinathrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 69

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of bifenthrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 70

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of cyhalothrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 71

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of lambda-cyhalothrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule,

Formulation Example 72

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of cypermethrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 73

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of deltamethrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 74

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of etofenprox, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 75

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of fenpropathrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 76

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of fenvalerate, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 77

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of esfenvalerate, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 78

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of permethrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 79

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of silafluofen, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 80

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of tefluthrin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 81

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of ethiprole, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 82

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of fipronil, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 83

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of ethiprole, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 84

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of fipronil, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 85

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of ethiprole, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 86

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of fipronil, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 87

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of ethiprole, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 88

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of fipronil, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 89

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of abamectin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 90

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of emamectin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 91

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of milbemectine, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 92

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of lepimectin, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 93

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of abamectin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 94

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of emamectin benzoate, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 95

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of milbemectine, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 96

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of lepimectin, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 97

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of abamectin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 98

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of emamectin benzoate, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 99

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of milbemectine, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 100

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of lepimectin, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 101

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of abamectin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 102

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of emamectin benzoate, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 103

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of milbemectine, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 104

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of lepimectin, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 105

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of the present diamide compound (2a), 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 106

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of chlorantraniliprole, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 107

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of the present diamide compound (2b), 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 108

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of the present diamide compound (2c), 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 109

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of flubendiamide, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 110

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of the present diamide compound (2a), 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 111

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of chlorantraniliprole, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 112

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of the present diamide compound (2b), 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 113

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of the present diamide compound (2c), 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 114

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of flubendiamide, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 115

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of the present diamide compound (2a), 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 116

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of chlorantraniliprole, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 117

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of the present diamide compound (2b), 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 118

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of the present diamide compound (2c), 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 119

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of flubendiamide, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 120

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of the present diamide compound (2a), 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 121

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of chlorantraniliprole, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 122

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of the present diamide compound (2b), 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 123

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of the present diamide compound (2c), 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 124

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of flubendiamide, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 125

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of pymetrozine, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 126

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of pyridalyl, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 127

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of pyriproxyfen, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 128

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of spirotetramat, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 129

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of sulfoxaflo, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 130

Five (5) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of flupyradifurone, 35 parts of a mixture (weight ratio 1:1) of white carbon and ammonium polyoxyethylene alkyl ether sulfate are mixed with an appropriate amount of water so as to give a total amount of 100 parts, and then the mixture is finely-ground by a wet grinding method to obtain each formulation.

Formulation Example 131

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of pymetrozine, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 132

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of pyridalyl, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 133

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of pyriproxyfen, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 134

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of spirotetramat, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 135

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of sulfoxaflo, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 136

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 2 parts of flupyradifurone, 1.5 parts of sorbitan trioleate, and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol are mixed, and then the mixture is finely-ground by a wet grinding method. To this mixture is added an appropriate amount of aqueous solution containing 0.05 parts of xanthane gum and 0.1 parts of magnesium aluminium silicate so as to give a total amount of 90 parts, and then 10 parts of propylene glycol is added thereto. The mixture is stirred to obtain each formulation.

Formulation Example 137

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of pymetrozine, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 138

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of pyridalyl, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 139

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of pyriproxyfen, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 140

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of spirotetramat, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 141

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of sulfoxaflo, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 142

Ten (10) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 10 parts of flupyradifurone, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the rest parts of synthetic hydrated silicon oxide are well mixed while grinding to obtain 100 parts of each wettable powder.

Formulation Example 143

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of pymetrozine, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 144

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of pyridalyl, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 145

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of pyriproxyfen, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 146

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of spirotetramat, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 147

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of sulfoxaflo, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Formulation Example 148

One (1) parts of one compound selected from the present fused heterocyclic compounds 1 to 481, 0.5 parts of flupyradifurone, 1 parts of synthetic hydrated silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and the rest parts of kaolin clay are mixed. Then, to this mixture is added a suitable amount of water, and the mixture is further stirred, granulated by a granulator, and dried under ventilation to obtain each granule.

Next, an efficacy of the composition for controlling pests of the present invention on controlling pests is shown in the test examples.

Test Example 1

One (1) mg of any one of the present fused heterocyclic compounds 3, 4, 5, 9, 15, 16, 17, 18, 19, 20, 22, 25, 27, 28, 29, 34, 36, 39, 48, 50, 53, 71, 72, 74, 81, 85, 89, 99, 130, 312, 399, 404, 409, 414, 419, 421, 423, 443, 444, 445, 464 and 467 was dissolved in 10 μL of mixed solvent of xylene, dimethylformamide, and surfactant (Trade name: Sorpol 3005X, manufactured by TOHO CHEMICAL INDUSTRY CO. LTD) (4:4:1 (volume ratio)). Then, the mixture was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give a given concentration.

Each commercial formulation of clothianidin (Trade name: Dantotsu water soluble powders, manufactured by Sumitomo Chemical Company, Limited), thiamethoxam (Trade name: ACTARA water-dispersible granule, manufactured by Syngenta), imidacloprid (Trade name: Admire wettable powder, manufactured by Bayer CropScience Ltd.), nitenpyram (Trade name: Bestgard water soluble powder, manufactured by Sumitomo Chemical Company, Limited) or dinotefuran (Trade name: Starkle water-dispersible granule, manufactured by Hokko Chemical Industry Co., Ltd) was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration.

The resulting water-diluted solution of the present fused heterocyclic compound and the resulting water-diluted solution of clothianidin, thiamethoxam, imidacloprid, nitenpyram or dinotefuran were mixed to prepare a test solution.

Leaf disks (1.5 cm in diameter) of cabbage (Brassicae oleracea) were placed in each well of 24-well microplates (manufactured by Becton Dickinson), and 40 μL of the test solution was applied per well (hereinafter, referred to as “treated group”). An untreated group was prepared by applying 40 μL of water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) only into a well.

After air drying, five diamondback moth (Plutella xylostella) (2nd instar larva) were released per well, and the wells were covered with a paper towel and then covered with a lid. At two days after the release, the number of surviving insects was counted on each well.

The mortality of the treated group and the mortality of the untreated group were calculated by the following equation 1), respectively. One replication test was performed on each group. Mortality (%)=(Total number of Tested insects−Number of Surviving insects)/Total number of Tested insects×100  Equation 1)

The results are shown in Tables 21 to 34.

TABLE 21 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 3 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 3 + clothianidin 500 + 500  100 Present fused heterocyclic compound 3 + clothianidin 500 + 50  100 Present fused heterocyclic compound 3 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 3 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 3 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 3 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 3 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 3 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 3 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 3 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 3 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 4 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 4 + clothianidin 500 + 500  100 Present fused heterocyclic compound 4 + clothianidin 500 + 50  100 Present fused heterocyclic compound 4 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 4 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 4 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 4 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 4 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 4 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 4 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 4 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 4 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 5 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 5 + clothianidin 500 + 500  100 Present fused heterocyclic compound 5 + clothianidin 500 + 50  100 Present fused heterocyclic compound 5 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 5 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 5 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 5 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 5 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 5 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 5 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 5 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 5 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 22 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 9 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 9 + clothianidin 500 + 500  100 Present fused heterocyclic compound 9 + clothianidin 500 + 50  100 Present fused heterocyclic compound 9 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 9 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 9 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 9 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 9 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 9 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 9 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 9 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 9 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 15 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 15 + clothianidin 500 + 500  100 Present fused heterocyclic compound 15 + clothianidin 500 + 50  100 Present fused heterocyclic compound 15 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 15 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 15 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 15 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 15 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 15 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 15 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 15 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 15 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 16 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 16 + clothianidin 500 + 500  100 Present fused heterocyclic compound 16 + clothianidin 500 + 50  100 Present fused heterocyclic compound 16 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 16 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 16 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 16 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 16 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 16 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 16 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 16 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 16 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 23 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 17 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 17 + clothianidin 500 + 500  100 Present fused heterocyclic compound 17 + clothianidin 500 + 50  100 Present fused heterocyclic compound 17 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 17 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 17 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 17 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 17 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 17 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 17 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 17 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 17 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 18 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 18 + clothianidin 500 + 500  100 Present fused heterocyclic compound 18 + clothianidin 500 + 50  100 Present fused heterocyclic compound 18 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 18 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 18 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 18 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 18 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 18 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 18 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 18 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 18 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 19 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 19 + clothianidin 500 + 500  100 Present fused heterocyclic compound 19 + clothianidin 500 + 50  100 Present fused heterocyclic compound 19 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 19 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 19 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 19 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 19 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 19 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 19 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 19 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 19 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 24 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 20 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 20 + clothianidin 500 + 500  100 Present fused heterocyclic compound 20 + clothianidin 500 + 50  100 Present fused heterocyclic compound 20 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 20 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 20 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 20 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 20 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 20 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 20 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 20 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 20 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 22 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 22 + clothianidin 500 + 500  100 Present fused heterocyclic compound 22 + clothianidin 500 + 50  100 Present fused heterocyclic compound 22 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 22 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 22 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 22 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 22 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 22 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 22 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 22 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 22 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 25 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 25 + clothianidin 500 + 500  100 Present fused heterocyclic compound 25 + clothianidin 500 + 50  100 Present fused heterocyclic compound 25 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 25 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 25 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 25 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 25 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 25 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 25 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 25 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 25 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 25 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 27 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 27 + clothianidin 500 + 500  100 Present fused heterocyclic compound 27 + clothianidin 500 + 50  100 Present fused heterocyclic compound 27 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 27 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 27 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 27 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 27 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 27 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 27 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 27 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 27 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 28 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 28 + clothianidin 500 + 500  100 Present fused heterocyclic compound 28 + clothianidin 500 + 50  100 Present fused heterocyclic compound 28 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 28 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 28 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 28 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 28 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 28 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 28 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 28 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 28 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 29 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 29 + clothianidin 500 + 500  100 Present fused heterocyclic compound 29 + clothianidin 500 + 50  100 Present fused heterocyclic compound 29 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 29 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 29 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 29 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 29 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 29 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 29 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 29 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 29 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 26 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 34 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 34 + clothianidin 500 + 500  100 Present fused heterocyclic compound 34 + clothianidin 500 + 50  100 Present fused heterocyclic compound 34 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 34 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 34 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 34 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 34 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 34 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 34 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 34 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 34 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 36 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 36 + clothianidin 500 + 500  100 Present fused heterocyclic compound 36 + clothianidin 500 + 50  100 Present fused heterocyclic compound 36 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 36 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 36 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 36 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 36 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 36 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 36 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 36 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 36 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 39 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 39 + clothianidin 500 + 500  100 Present fused heterocyclic compound 39 + clothianidin 500 + 50  100 Present fused heterocyclic compound 39 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 39 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 39 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 39 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 39 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 39 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 39 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 39 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 39 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 27 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 48 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 48 + clothianidin 500 + 500  100 Present fused heterocyclic compound 48 + clothianidin 500 + 50  100 Present fused heterocyclic compound 48 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 48 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 48 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 48 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 48 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 48 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 48 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 48 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 48 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 50 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 50 + clothianidin 500 + 500  100 Present fused heterocyclic compound 50 + clothianidin 500 + 50  100 Present fused heterocyclic compound 50 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 50 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 50 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 50 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 50 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 50 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 50 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 50 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 50 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 53 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 53 + clothianidin 500 + 500  100 Present fused heterocyclic compound 53 + clothianidin 500 + 50  100 Present fused heterocyclic compound 53 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 53 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 53 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 53 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 53 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 53 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 53 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 53 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 53 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 28 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 71 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 71 + clothianidin 500 + 500  100 Present fused heterocyclic compound 71 + clothianidin 500 + 50  100 Present fused heterocyclic compound 71 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 71 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 71 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 71 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 71 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 71 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 71 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 71 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 71 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 72 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 72 + clothianidin 500 + 500  100 Present fused heterocyclic compound 72 + clothianidin 500 + 50  100 Present fused heterocyclic compound 72 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 72 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 72 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 72 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 72 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 72 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 72 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 72 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 72 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 74 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 74 + clothianidin 500 + 500  100 Present fused heterocyclic compound 74 + clothianidin 500 + 50  100 Present fused heterocyclic compound 74 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 74 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 74 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 74 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 74 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 74 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 74 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 74 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 74 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 29 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 81 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 81 + clothianidin 500 + 500  100 Present fused heterocyclic compound 81 + clothianidin 500 + 50  100 Present fused heterocyclic compound 81 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 81 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 81 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 81 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 81 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 81 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 81 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 81 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 81 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 85 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 85 + clothianidin 500 + 500  100 Present fused heterocyclic compound 85 + clothianidin 500 + 50  100 Present fused heterocyclic compound 85 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 85 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 85 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 85 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 85 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 85 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 85 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 85 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 85 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 89 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 89 + clothianidin 500 + 500  100 Present fused heterocyclic compound 89 + clothianidin 500 + 50  100 Present fused heterocyclic compound 89 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 89 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 89 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 89 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 89 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 89 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 89 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 89 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 89 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 30 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 99 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 99 + clothianidin 500 + 500  100 Present fused heterocyclic compound 99 + clothianidin 500 + 50  100 Present fused heterocyclic compound 99 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 99 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 99 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 99 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 99 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 99 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 99 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 99 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 99 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 130 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 130 + clothianidin 500 + 500  100 Present fused heterocyclic compound 130 + clothianidin 500 + 50  100 Present fused heterocyclic compound 130 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 130 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 130 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 130 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 130 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 130 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 130 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 130 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 130 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 312 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 312 + clothianidin 500 + 500  100 Present fused heterocyclic compound 312 + clothianidin 500 + 50  100 Present fused heterocyclic compound 312 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 312 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 312 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 312 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 312 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 312 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 312 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 312 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 312 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 31 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 399 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 399 + clothianidin 500 + 500  100 Present fused heterocyclic compound 399 + clothianidin 500 + 50  100 Present fused heterocyclic compound 399 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 399 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 399 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 399 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 399 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 399 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 399 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 399 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 399 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 404 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 404 + clothianidin 500 + 500  100 Present fused heterocyclic compound 404 + clothianidin 500 + 50  100 Present fused heterocyclic compound 404 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 404 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 404 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 404 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 404 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 404 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 404 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 404 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 404 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 409 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 409 + clothianidin 500 + 500  100 Present fused heterocyclic compound 409 + clothianidin 500 + 50  100 Present fused heterocyclic compound 409 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 409 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 409 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 409 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 409 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 409 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 409 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 409 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 409 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 32 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 414 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 414 + clothianidin 500 + 500  100 Present fused heterocyclic compound 414 + clothianidin 500 + 50  100 Present fused heterocyclic compound 414 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 414 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 414 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 414 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 414 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 414 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 414 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 414 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 414 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 419 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 419 + clothianidin 500 + 500  100 Present fused heterocyclic compound 419 + clothianidin 500 + 50  100 Present fused heterocyclic compound 419 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 419 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 419 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 419 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 419 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 419 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 419 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 419 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 419 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 421 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 421 + clothianidin 500 + 500  100 Present fused heterocyclic compound 421 + clothianidin 500 + 50  100 Present fused heterocyclic compound 421 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 421 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 421 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 421 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 421 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 421 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 421 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 421 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 421 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 33 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 423 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 423 + clothianidin 500 + 500  100 Present fused heterocyclic compound 423 + clothianidin 500 + 50  100 Present fused heterocyclic compound 423 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 423 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 423 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 423 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 423 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 423 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 423 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 423 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 423 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 443 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 443 + clothianidin 500 + 500  100 Present fused heterocyclic compound 443 + clothianidin 500 + 50  100 Present fused heterocyclic compound 443 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 443 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 443 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 443 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 443 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 443 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 443 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 443 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 443 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 444 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 444 + clothianidin 500 + 500  100 Present fused heterocyclic compound 444 + clothianidin 500 + 50  100 Present fused heterocyclic compound 444 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 444 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 444 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 444 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 444 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 444 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 444 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 444 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 444 + dinotefuran 500 + 50  100 Untreated group — 0

TABLE 34 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 445 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 445 + clothianidin 500 + 500  100 Present fused heterocyclic compound 445 + clothianidin 500 + 50  100 Present fused heterocyclic compound 445 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 445 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 445 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 445 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 445 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 445 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 445 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 445 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 445 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 464 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 464 + clothianidin 500 + 500  100 Present fused heterocyclic compound 464 + clothianidin 500 + 50  100 Present fused heterocyclic compound 464 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 464 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 464 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 464 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 464 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 464 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 464 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 464 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 464 + dinotefuran 500 + 50  100 Present fused heterocyclic compound 467 + clothianidin 200 + 2000 100 Present fused heterocyclic compound 467 + clothianidin 500 + 500  100 Present fused heterocyclic compound 467 + clothianidin 500 + 50  100 Present fused heterocyclic compound 467 + thiamethoxam 200 + 2000 100 Present fused heterocyclic compound 467 + thiamethoxam 500 + 500  100 Present fused heterocyclic compound 467 + thiamethoxam 500 + 50  100 Present fused heterocyclic compound 467 + imidacloprid 200 + 2000 100 Present fused heterocyclic compound 467 + imidacloprid 500 + 50  100 Present fused heterocyclic compound 467 + nitenpyram 200 + 2000 100 Present fused heterocyclic compound 467 + nitenpyram 500 + 50  100 Present fused heterocyclic compound 467 + dinotefuran 200 + 2000 100 Present fused heterocyclic compound 467 + dinotefuran 500 + 50  100 Untreated group — 0

Test Example 2

One (1) mg of any one of the present fused heterocyclic compounds 3, 4, 5, 9, 15, 16, 17, 18, 19, 20, 22, 25, 27, 28, 29, 34, 36, 39, 48, 50, 53, 71, 72, 74, 81, 85, 89, 99, 130, 312, 399, 404, 409, 414, 419, 421, 423, 443, 444, 445, 464 and 467 was dissolved in 10 μL of mixed solvent of xylene, dimethylformamide, and surfactant (Trade name: Sorpol 3005X, manufactured by TOHO CHEMICAL INDUSTRY CO. LTD) (4:4:1 (volume ratio)). Then, the mixture was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give a given concentration.

Each commercial formulation of esfenvalerate (Trade name: SUMI ALPHA 5 EC, manufactured by Sumitomo Chemical Company, Limited) and fenpropathrin (Trade name: Roddy emulsion, manufactured by Sumitomo Chemical Company, Limited) was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration.

One (1) mg of Lambda-cyhalothrin (manufactured by Kanto Chemical Co., Inc.) was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration.

The resulting water-diluted solution of the present fused heterocyclic compound and the resulting water-diluted solution of esfenvalerate, fenpropathrin or Lambda-cyhalothrin were mixed to prepare a test solution.

Leaf disks (1.5 cm in diameter) of cabbage (Brassicae oleracea) were placed in each well of 24-well microplates (manufactured by Becton Dickinson), and 40 μL of the test solution was applied per well (hereinafter, referred to as “treated group”). An untreated group was prepared by applying 40 μL of water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) only into a well.

After air drying, five diamondback moth (Plutella xylostella) (2nd instar larva) were released per well, and the wells were covered with a paper towel and then covered with a lid. At two days after the release, the number of surviving insects was counted on each well.

The mortality of the treated group and the mortality of the untreated group were calculated by the following equation 1), respectively. One replication test was performed on each group. Mortality (%)=(Total number of Tested insects−Number of Surviving insects)/Total number of Tested insects×100  Equation 1)

The results are shown in Tables 35 to 41.

TABLE 35 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 3 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 3 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 3 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 3 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 3 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 3 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 4 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 4 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 4 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 4 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 4 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 4 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 5 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 5 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 5 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 5 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 5 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 5 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 9 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 9 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 9 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 9 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 9 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 9 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 15 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 15 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 15 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 15 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 15 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 15 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 16 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 16 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 16 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 16 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 16 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 16 + lambda-cyhalothrin 500 + 50  100 Untreated group — 0

TABLE 36 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 17 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 17 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 17 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 17 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 17 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 17 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 18 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 18 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 18 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 18 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 18 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 18 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 19 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 19 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 19 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 19 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 19 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 19 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 20 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 20 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 20 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 20 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 20 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 20 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 22 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 22 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 22 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 22 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 22 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 22 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 25 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 25 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 25 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 25 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 25 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 25 + lambda-cyhalothrin 500 + 50  100 Untreated group — 0

TABLE 37 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 27 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 27 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 27 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 27 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 27 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 27 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 28 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 28 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 28 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 28 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 28 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 28 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 29 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 29 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 29 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 29 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 29 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 29 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 34 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 34 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 34 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 34 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 34 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 34 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 36 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 36 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 36 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 36 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 36 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 36 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 39 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 39 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 39 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 39 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 39 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 39 + lambda-cyhalothrin 500 + 50  100 Untreated group — 0

TABLE 38 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 48 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 48 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 48 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 48 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 48 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 48 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 50 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 50 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 50 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 50 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 50 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 50 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 53 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 53 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 53 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 53 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 53 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 53 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 71 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 71 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 71 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 71 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 71 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 71 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 72 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 72 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 72 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 72 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 72 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 72 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 74 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 74 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 74 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 74 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 74 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 74 + lambda-cyhalothrin 500 + 50  100 Untreated group — 0

TABLE 39 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 81 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 81 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 81 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 81 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 81 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 81 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 85 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 85 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 85 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 85 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 85 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 85 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 89 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 89 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 89 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 89 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 89 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 89 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 99 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 99 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 99 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 99 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 99 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 99 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 130 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 130 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 130 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 130 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 130 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 130 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 312 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 312 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 312 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 312 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 312 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 312 + lambda-cyhalothrin 500 + 50  100 Untreated group — 0

TABLE 40 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 399 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 399 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 399 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 399 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 399 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 399 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 404 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 404 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 404 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 404 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 404 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 404 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 409 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 409 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 409 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 409 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 409 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 409 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 414 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 414 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 414 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 414 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 414 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 414 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 419 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 419 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 419 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 419 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 419 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 419 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 421 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 421 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 421 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 421 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 421 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 421 + lambda-cyhalothrin 500 + 50  100 Untreated group — 0

TABLE 41 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 423 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 423 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 423 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 423 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 423 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 423 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 443 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 443 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 443 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 443 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 443 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 443 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 444 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 444 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 444 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 444 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 444 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 444 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 445 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 445 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 445 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 445 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 445 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 445 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 464 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 464 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 464 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 464 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 464 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 464 + lambda-cyhalothrin 500 + 50  100 Present fused heterocyclic compound 467 + esfenvalerate 200 + 2000 100 Present fused heterocyclic compound 467 + esfenvalerate 500 + 50  100 Present fused heterocyclic compound 467 + fenpropathrin 200 + 2000 100 Present fused heterocyclic compound 467 + fenpropathrin 500 + 50  100 Present fused heterocyclic compound 467 + lambda-cyhalothrin 200 + 2000 100 Present fused heterocyclic compound 467 + lambda-cyhalothrin 500 + 50  100 Untreated group — 0

Test Example 3

One (1) mg of any one of the present fused heterocyclic compounds 3, 4, 5, 9, 15, 16, 17, 18, 19, 20, 22, 25, 27, 28, 29, 34, 36, 39, 48, 50, 53, 71, 72, 74, 81, 85, 89, 99, 130, 312, 399, 404, 409, 414, 419, 421, 423, 443, 444, 445, 464 and 467 was dissolved in 10 μL of mixed solvent of xylene, dimethylformamide, and surfactant (Trade name: Sorpol 3005X, manufactured by TOHO CHEMICAL INDUSTRY CO. LTD) (4:4:1 (volume ratio)). Then, the mixture was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give a given concentration.

Each commercial formulation of fipronil (Trade name: Prince Flowable, manufactured by BASF Agro) and ethiprole (Trade name: Key Wrap Flowable, manufactured by Hokko Chemical Industry) was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration.

The resulting water-diluted solution of the present fused heterocyclic compound and the resulting water-diluted solution of fipronil or ethiprole were mixed to prepare a test solution.

Leaf disks (1.5 cm in diameter) of cabbage (Brassicae oleracea) were placed in each well of 24-well microplates (manufactured by Becton Dickinson), and 40 μL of the test solution was applied per well (hereinafter, referred to as “treated group”). An untreated group was prepared by applying 40 μL of water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) only into a well.

After air drying, five diamondback moth (Plutella xylostella) (2nd instar larva) were released per well, and the wells were covered with a paper towel and then covered with a lid. At two days after the release, the number of surviving insects was counted on each well.

The mortality of the treated group and the mortality of the untreated group were calculated by the following equation 1), respectively. One replication test was performed on each group. Mortality (%)=(Total number of Tested insects−Number of Surviving insects)/Total number of Tested insects×100  Equation 1)

The results are shown in Tables 42 to 46.

TABLE 42 Concen- Mor- tration tality Composition (ppm) (%) Present fused heterocyclic compound 3 + fipronil 200 + 2000 100 Present fused heterocyclic compound 3 + fipronil 500 + 50  100 Present fused heterocyclic compound 3 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 3 + ethiprole 500 + 50  100 Present fused heterocyclic compound 4 + fipronil 200 + 2000 100 Present fused heterocyclic compound 4 + fipronil 500 + 50  100 Present fused heterocyclic compound 4 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 4 + ethiprole 500 + 50  100 Present fused heterocyclic compound 5 + fipronil 200 + 2000 100 Present fused heterocyclic compound 5 + fipronil 500 + 50  100 Present fused heterocyclic compound 5 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 5 + ethiprole 500 + 50  100 Present fused heterocyclic compound 9 + fipronil 200 + 2000 100 Present fused heterocyclic compound 9 + fipronil 500 + 50  100 Present fused heterocyclic compound 9 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 9 + ethiprole 500 + 50  100 Present fused heterocyclic compound 15 + fipronil 200 + 2000 100 Present fused heterocyclic compound 15 + fipronil 500 + 50  100 Present fused heterocyclic compound 15 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 15 + ethiprole 500 + 50  100 Present fused heterocyclic compound 16 + fipronil 200 + 2000 100 Present fused heterocyclic compound 16 + fipronil 500 + 50  100 Present fused heterocyclic compound 16 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 16 + ethiprole 500 + 50  100 Present fused heterocyclic compound 17 + fipronil 200 + 2000 100 Present fused heterocyclic compound 17 + fipronil 500 + 50  100 Present fused heterocyclic compound 17 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 17 + ethiprole 500 + 50  100 Present fused heterocyclic compound 18 + fipronil 200 + 2000 100 Present fused heterocyclic compound 18 + fipronil 500 + 50  100 Present fused heterocyclic compound 18 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 18 + ethiprole 500 + 50  100 Present fused heterocyclic compound 19 + fipronil 200 + 2000 100 Present fused heterocyclic compound 19 + fipronil 500 + 50  100 Present fused heterocyclic compound 19 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 19 + ethiprole 500 + 50  100 Untreated group — 0

TABLE 43 Concen- Mor- tration tality Composition (ppm) (%) Present fused heterocyclic compound 20 + fipronil 200 + 2000 100 Present fused heterocyclic compound 20 + fipronil 500 + 50  100 Present fused heterocyclic compound 20 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 20 + ethiprole 500 + 50  100 Present fused heterocyclic compound 22 + fipronil 200 + 2000 100 Present fused heterocyclic compound 22 + fipronil 500 + 50  100 Present fused heterocyclic compound 22 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 22 + ethiprole 500 + 50  100 Present fused heterocyclic compound 25 + fipronil 200 + 2000 100 Present fused heterocyclic compound 25 + fipronil 500 + 50  100 Present fused heterocyclic compound 25 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 25 + ethiprole 500 + 50  100 Present fused heterocyclic compound 27 + fipronil 200 + 2000 100 Present fused heterocyclic compound 27 + fipronil 500 + 50  100 Present fused heterocyclic compound 27 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 27 + ethiprole 500 + 50  100 Present fused heterocyclic compound 28 + fipronil 200 + 2000 100 Present fused heterocyclic compound 28 + fipronil 500 + 50  100 Present fused heterocyclic compound 28 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 28 + ethiprole 500 + 50  100 Present fused heterocyclic compound 29 + fipronil 200 + 2000 100 Present fused heterocyclic compound 29 + fipronil 500 + 50  100 Present fused heterocyclic compound 29 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 29 + ethiprole 500 + 50  100 Present fused heterocyclic compound 34 + fipronil 200 + 2000 100 Present fused heterocyclic compound 34 + fipronil 500 + 50  100 Present fused heterocyclic compound 34 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 34 + ethiprole 500 + 50  100 Present fused heterocyclic compound 36 + fipronil 200 + 2000 100 Present fused heterocyclic compound 36 + fipronil 500 + 50  100 Present fused heterocyclic compound 36 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 36 + ethiprole 500 + 50  100 Present fused heterocyclic compound 39 + fipronil 200 + 2000 100 Present fused heterocyclic compound 39 + fipronil 500 + 50  100 Present fused heterocyclic compound 39 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 39 + ethiprole 500 + 50  100 Untreated group — 0

TABLE 44 Concen- Mor- tration tality Composition (ppm) (%) Present fused heterocyclic compound 48 + fipronil 200 + 2000 100 Present fused heterocyclic compound 48 + fipronil 500 + 50  100 Present fused heterocyclic compound 48 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 48 + ethiprole 500 + 50  100 Present fused heterocyclic compound 50 + fipronil 200 + 2000 100 Present fused heterocyclic compound 50 + fipronil 500 + 50  100 Present fused heterocyclic compound 50 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 50 + ethiprole 500 + 50  100 Present fused heterocyclic compound 53 + fipronil 200 + 2000 100 Present fused heterocyclic compound 53 + fipronil 500 + 50  100 Present fused heterocyclic compound 53 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 53 + ethiprole 500 + 50  100 Present fused heterocyclic compound 71 + fipronil 200 + 2000 100 Present fused heterocyclic compound 71 + fipronil 500 + 50  100 Present fused heterocyclic compound 71 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 71 + ethiprole 500 + 50  100 Present fused heterocyclic compound 72 + fipronil 200 + 2000 100 Present fused heterocyclic compound 72 + fipronil 500 + 50  100 Present fused heterocyclic compound 72 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 72 + ethiprole 500 + 50  100 Present fused heterocyclic compound 74 + fipronil 200 + 2000 100 Present fused heterocyclic compound 74 + fipronil 500 + 50  100 Present fused heterocyclic compound 74 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 74 + ethiprole 500 + 50  100 Present fused heterocyclic compound 81 + fipronil 200 + 2000 100 Present fused heterocyclic compound 81 + fipronil 500 + 50  100 Present fused heterocyclic compound 81 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 81 + ethiprole 500 + 50  100 Present fused heterocyclic compound 85 + fipronil 200 + 2000 100 Present fused heterocyclic compound 85 + fipronil 500 + 50  100 Present fused heterocyclic compound 85 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 85 + ethiprole 500 + 50  100 Present fused heterocyclic compound 89 + fipronil 200 + 2000 100 Present fused heterocyclic compound 89 + fipronil 500 + 50  100 Present fused heterocyclic compound 89 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 89 + ethiprole 500 + 50  100 Untreated group — 0

TABLE 45 Concentration Composition (ppm) Mortality (%) Present fused heterocyclic compound 99 + fipronil 200 + 2000 100 Present fused heterocyclic compound 99 + fipronil 500 + 50  100 Present fused heterocyclic compound 99 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 99 + ethiprole 500 + 50  100 Present fused heterocyclic compound 130 + fipronil 200 + 2000 100 Present fused heterocyclic compound 130 + fipronil 500 + 50  100 Present fused heterocyclic compound 130 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 130 + ethiprole 500 + 50  100 Present fused heterocyclic compound 312 + fipronil 200 + 2000 100 Present fused heterocyclic compound 312 + fipronil 500 + 50  100 Present fused heterocyclic compound 312 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 312 + ethiprole 500 + 50  100 Present fused heterocyclic compound 399 + fipronil 200 + 2000 100 Present fused heterocyclic compound 399 + fipronil 500 + 50  100 Present fused heterocyclic compound 399 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 399 + ethiprole 500 + 50  100 Present fused heterocyclic compound 404 + fipronil 200 + 2000 100 Present fused heterocyclic compound 404 + fipronil 500 + 50  100 Present fused heterocyclic compound 404 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 404 + ethiprole 500 + 50  100 Present fused heterocyclic compound 409 + fipronil 200 + 2000 100 Present fused heterocyclic compound 409 + fipronil 500 + 50  100 Present fused heterocyclic compound 409 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 409 + ethiprole 500 + 50  100 Present fused heterocyclic compound 414 + fipronil 200 + 2000 100 Present fused heterocyclic compound 414 + fipronil 500 + 50  100 Present fused heterocyclic compound 414 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 414 + ethiprole 500 + 50  100 Present fused heterocyclic compound 419 + fipronil 200 + 2000 100 Present fused heterocyclic compound 419 + fipronil 500 + 50  100 Present fused heterocyclic compound 419 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 419 + ethiprole 500 + 50  100 Present fused heterocyclic compound 421 + fipronil 200 + 2000 100 Present fused heterocyclic compound 421 + fipronil 500 + 50  100 Present fused heterocyclic compound 421 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 421 + ethiprole 500 + 50  100 Untreated group — 0

TABLE 46 Concentration Composition (ppm) Mortality (%) Present fused heterocyclic compound 423 + fipronil 200 + 2000 100 Present fused heterocyclic compound 423 + fipronil 500 + 50  100 Present fused heterocyclic compound 423 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 423 + ethiprole 500 + 50  100 Present fused heterocyclic compound 443 + fipronil 200 + 2000 100 Present fused heterocyclic compound 443 + fipronil 500 + 50  100 Present fused heterocyclic compound 443 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 443 + ethiprole 500 + 50  100 Present fused heterocyclic compound 444 + fipronil 200 + 2000 100 Present fused heterocyclic compound 444 + fipronil 500 + 50  100 Present fused heterocyclic compound 444 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 444 + ethiprole 500 + 50  100 Present fused heterocyclic compound 445 + fipronil 200 + 2000 100 Present fused heterocyclic compound 445 + fipronil 500 + 50  100 Present fused heterocyclic compound 445 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 445 + ethiprole 500 + 50  100 Present fused heterocyclic compound 464 + fipronil 200 + 2000 100 Present fused heterocyclic compound 464 + fipronil 500 + 50  100 Present fused heterocyclic compound 464 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 464 + ethiprole 500 + 50  100 Present fused heterocyclic compound 467 + fipronil 200 + 2000 100 Present fused heterocyclic compound 467 + fipronil 500 + 50  100 Present fused heterocyclic compound 467 + ethiprole 200 + 2000 100 Present fused heterocyclic compound 467 + ethiprole 500 + 50  100 Untreated group — 0

Test Example 4

One (1) mg of any one of the present fused heterocyclic compounds 3, 4, 5, 9, 15, 16, 17, 18, 19, 20, 22, 25, 27, 28, 29, 34, 36, 39, 48, 50, 53, 71, 72, 74, 81, 85, 89, 99, 130, 312, 399, 404, 409, 414, 419, 421, 423, 443, 444, 445, 464 and 467 was dissolved in 10 μL of mixed solvent of xylene, dimethylformamide, and surfactant (Trade name: Sorpol 3005X, manufactured by TOHO CHEMICAL INDUSTRY CO. LTD) (4:4:1 (volume ratio)). Then, the mixture was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give a given concentration.

A commercial formulation of abamectin (Trade name: Agri-Mek 0.15EC, manufactured by Syngenta) was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration. The resulting water-diluted solution of the present fused heterocyclic compound and the resulting water-diluted solution of fipronil or ethiprole were mixed to prepare a test solution.

Leaf disks (1.5 cm in diameter) of cabbage (Brassicae oleracea) were placed in each well of 24-well microplates (manufactured by Becton Dickinson), and 40 μL of the test solution was applied per well (hereinafter, referred to as “treated group”). An untreated group was prepared by applying 40 μL of water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) only into a well.

After air drying, five diamondback moth (Plutella xylostella) (2nd instar larva) were released per well, and the wells were covered with a paper towel and then covered with a lid. At two days after the release, the number of surviving insects was counted on each well.

The mortality of the treated group and the mortality of the untreated group were calculated by the following equation 1), respectively. One replication test was performed on each group. Mortality (%)=(Total number of Tested insects−Number of Surviving insects)/Total number of Tested insects×100  Equation 1)

The results are shown in Tables 47 to 49.

TABLE 47 Concentration Composition (ppm) Mortality (%) Present fused heterocyclic compound 3 + abamectin 200 + 2000 100 Present fused heterocyclic compound 3 + abamectin 500 + 50  100 Present fused heterocyclic compound 4 + abamectin 200 + 2000 100 Present fused heterocyclic compound 4 + abamectin 500 + 50  100 Present fused heterocyclic compound 5 + abamectin 200 + 2000 100 Present fused heterocyclic compound 5 + abamectin 500 + 50  100 Present fused heterocyclic compound 9 + abamectin 200 + 2000 100 Present fused heterocyclic compound 9 + abamectin 500 + 50  100 Present fused heterocyclic compound 15 + abamectin 200 + 2000 100 Present fused heterocyclic compound 15 + abamectin 500 + 50  100 Present fused heterocyclic compound 16 + abamectin 200 + 2000 100 Present fused heterocyclic compound 16 + abamectin 500 + 50  100 Present fused heterocyclic compound 17 + abamectin 200 + 2000 100 Present fused heterocyclic compound 17 + abamectin 500 + 50  100 Present fused heterocyclic compound 18 + abamectin 200 + 2000 100 Present fused heterocyclic compound 18 + abamectin 500 + 50  100 Present fused heterocyclic compound 19 + abamectin 200 + 2000 100 Present fused heterocyclic compound 19 + abamectin 500 + 50  100 Present fused heterocyclic compound 20 + abamectin 200 + 2000 100 Present fused heterocyclic compound 20 + abamectin 500 + 50  100 Present fused heterocyclic compound 22 + abamectin 200 + 2000 100 Present fused heterocyclic compound 22 + abamectin 500 + 50  100 Present fused heterocyclic compound 25 + abamectin 200 + 2000 100 Present fused heterocyclic compound 25 + abamectin 500 + 50  100 Present fused heterocyclic compound 27 + abamectin 200 + 2000 100 Present fused heterocyclic compound 27 + abamectin 500 + 50  100 Present fused heterocyclic compound 28 + abamectin 200 + 2000 100 Present fused heterocyclic compound 28 + abamectin 500 + 50  100 Present fused heterocyclic compound 29 + abamectin 200 + 2000 100 Present fused heterocyclic compound 29 + abamectin 500 + 50  100 Present fused heterocyclic compound 34 + abamectin 200 + 2000 100 Present fused heterocyclic compound 34 + abamectin 500 + 50  100 Present fused heterocyclic compound 36 + abamectin 200 + 2000 100 Present fused heterocyclic compound 36 + abamectin 500 + 50  100 Untreated group — 0

TABLE 48 Concentration Composition (ppm) Mortality (%) Present fused heterocyclic compound 39 + abamectin 200 + 2000 100 Present fused heterocyclic compound 39 + abamectin 500 + 50  100 Present fused heterocyclic compound 48 + abamectin 200 + 2000 100 Present fused heterocyclic compound 48 + abamectin 500 + 50  100 Present fused heterocyclic compound 50 + abamectin 200 + 2000 100 Present fused heterocyclic compound 50 + abamectin 500 + 50  100 Present fused heterocyclic compound 53 + abamectin 200 + 2000 100 Present fused heterocyclic compound 53 + abamectin 500 + 50  100 Present fused heterocyclic compound 71 + abamectin 200 + 2000 100 Present fused heterocyclic compound 71 + abamectin 500 + 50  100 Present fused heterocyclic compound 72 + abamectin 200 + 2000 100 Present fused heterocyclic compound 72 + abamectin 500 + 50  100 Present fused heterocyclic compound 74 + abamectin 200 + 2000 100 Present fused heterocyclic compound 74 + abamectin 500 + 50  100 Present fused heterocyclic compound 81 + abamectin 200 + 2000 100 Present fused heterocyclic compound 81 + abamectin 500 + 50  100 Present fused heterocyclic compound 85 + abamectin 200 + 2000 100 Present fused heterocyclic compound 85 + abamectin 500 + 50  100 Present fused heterocyclic compound 89 + abamectin 200 + 2000 100 Present fused heterocyclic compound 89 + abamectin 500 + 50  100 Present fused heterocyclic compound 99 + abamectin 200 + 2000 100 Present fused heterocyclic compound 99 + abamectin 500 + 50  100 Present fused heterocyclic compound 130 + abamectin 200 + 2000 100 Present fused heterocyclic compound 130 + abamectin 500 + 50  100 Present fused heterocyclic compound 312 + abamectin 200 + 2000 100 Present fused heterocyclic compound 312 + abamectin 500 + 50  100 Present fused heterocyclic compound 399 + abamectin 200 + 2000 100 Present fused heterocyclic compound 399 + abamectin 500 + 50  100 Present fused heterocyclic compound 404 + abamectin 200 + 2000 100 Present fused heterocyclic compound 404 + abamectin 500 + 50  100 Present fused heterocyclic compound 409 + abamectin 200 + 2000 100 Present fused heterocyclic compound 409 + abamectin 500 + 50  100 Present fused heterocyclic compound 414 + abamectin 200 + 2000 100 Present fused heterocyclic compound 414 + abamectin 500 + 50  100 Untreated group — 0

TABLE 49 Concentration Composition (ppm) Mortality (%) Present fused heterocyclic compound 419 + abamectin 200 + 2000 100 Present fused heterocyclic compound 419 + abamectin 500 + 50  100 Present fused heterocyclic compound 421 + abamectin 200 + 2000 100 Present fused heterocyclic compound 421 + abamectin 500 + 50  100 Present fused heterocyclic compound 423 + abamectin 200 + 2000 100 Present fused heterocyclic compound 423 + abamectin 500 + 50  100 Present fused heterocyclic compound 443 + abamectin 200 + 2000 100 Present fused heterocyclic compound 443 + abamectin 500 + 50  100 Present fused heterocyclic compound 444 + abamectin 200 + 2000 100 Present fused heterocyclic compound 444 + abamectin 500 + 50  100 Present fused heterocyclic compound 445 + abamectin 200 + 2000 100 Present fused heterocyclic compound 445 + abamectin 500 + 50  100 Present fused heterocyclic compound 464 + abamectin 200 + 2000 100 Present fused heterocyclic compound 464 + abamectin 500 + 50  100 Present fused heterocyclic compound 467 + abamectin 200 + 2000 100 Present fused heterocyclic compound 467 + abamectin 500 + 50  100 Untreated group — 0

Test Example 5

One (1) mg of any one of the present fused heterocyclic compounds 3, 4, 5, 9, 15, 16, 17, 18, 19, 20, 22, 25, 27, 28, 29, 34, 36, 39, 48, 50, 53, 71, 72, 74, 81, 85, 89, 99, 130, 312, 399, 404, 409, 414, 419, 421, 423, 443, 444, 445, 464 and 467 was dissolved in 10 μL of mixed solvent of xylene, dimethylformamide, and surfactant (Trade name: Sorpol 3005X, manufactured by TOHO CHEMICAL INDUSTRY CO. LTD) (4:4:1 (volume ratio)). Then, the mixture was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give a given concentration.

A commercial formulation of chlorantraniliprole (Prevathon Flowable 5, manufactured by DuPont) was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration. Each of 1 mg of the present diamide compound (2b) and the present diamide compound (2c) was dissolved in 10 μL of mixed solvent of xylene, dimethylformamide, and surfactant (Trade name: Sorpol 3005X, manufactured by TOHO CHEMICAL INDUSTRY CO. LTD) (4:4:1 (volume ratio)), and was then diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration.

The resulting water-diluted solution of the present fused heterocyclic compound and the resulting water-diluted solution of chlorantraniliprole, the present diamide compound (2b) or the present diamide compound (2c) were mixed to prepare a test solution.

Leaf disks (1.5 cm in diameter) of cabbage (Brassicae oleracea) were placed in each well of 24-well microplates (manufactured by Becton Dickinson), and 40 μL of the test solution was applied per well (hereinafter, referred to as “treated group”). An untreated group was prepared by applying 40 μL of water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) only into a well.

After air drying, five diamondback moth (Plutella xylostella) (2nd instar larva) were released per well, and the wells were covered with a paper towel and then covered with a lid. At two days after the release, the number of surviving insects was counted on each well.

The mortality of the treated group and the mortality of the untreated group were calculated by the following equation 1), respectively. One replication test was performed on each group. Mortality (%)=(Total number of Tested insects−Number of Surviving insects)/Total number of Tested insects 100  Equation 1)

The results are shown in Tables 50 to 60.

TABLE 50 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 3 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 3 + chlorantraniliprole 500 + 500  100 Present fused heterocyclic compound 3 + chlorantraniliprole 500 + 50  100 Present fused heterocyclic compound 3 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 3 + diamide compound (2b) 500 + 500  100 Present fused heterocyclic compound 3 + diamide compound (2b) 500 + 50  100 Present fused heterocyclic compound 3 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 3 + diamide compound (2c) 500 + 50  100 Present fused heterocyclic compound 4 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 4 + chlorantraniliprole 500 + 500  100 Present fused heterocyclic compound 4 + chlorantraniliprole 500 + 50  100 Present fused heterocyclic compound 4 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 4 + diamide compound (2b) 500 + 500  100 Present fused heterocyclic compound 4 + diamide compound (2b) 500 + 50  100 Present fused heterocyclic compound 4 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 4 + diamide compound (2c) 500 + 50  100 Present fused heterocyclic compound 5 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 5 + chlorantraniliprole 500 + 500  100 Present fused heterocyclic compound 5 + chlorantraniliprole 500 + 50  100 Present fused heterocyclic compound 5 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 5 + diamide compound (2b) 500 + 500  100 Present fused heterocyclic compound 5 + diamide compound (2b) 500 + 50  100 Present fused heterocyclic compound 5 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 5 + diamide compound (2c) 500 + 50  100 Present fused heterocyclic compound 9 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 9 + chlorantraniliprole 500 + 500  100 Present fused heterocyclic compound 9 + chlorantraniliprole 500 + 50  100 Present fused heterocyclic compound 9 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 9 + diamide compound (2b) 500 + 500  100 Present fused heterocyclic compound 9 + diamide compound (2b) 500 + 50  100 Present fused heterocyclic compound 9 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 9 + diamide compound (2c) 500 + 50  100 Untreated group — 0

TABLE 51 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 15 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 15 + chlorantraniliprole 500 + 500  100 Present fused heterocyclic compound 15 + chlorantraniliprole 500 + 50  100 Present fused heterocyclic compound 15 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 15 + diamide compound (2b) 500 + 500  100 Present fused heterocyclic compound 15 + diamide compound (2b) 500 + 50  100 Present fused heterocyclic compound 15 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 15 + diamide compound (2c) 500 + 50  100 Present fused heterocyclic compound 16 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 16 + chlorantraniliprole 500 + 500  100 Present fused heterocyclic compound 16 + chlorantraniliprole 500 + 50  100 Present fused heterocyclic compound 16 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 16 + diamide compound (2b) 500 + 500  100 Present fused heterocyclic compound 16 + diamide compound (2b) 500 + 50  100 Present fused heterocyclic compound 16 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 16 + diamide compound (2c) 500 + 50  100 Present fused heterocyclic compound 17 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 17 + chlorantraniliprole 500 + 500  100 Present fused heterocyclic compound 17 + chlorantraniliprole 500 + 50  100 Present fused heterocyclic compound 17 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 17 + diamide compound (2b) 500 + 500  100 Present fused heterocyclic compound 17 + diamide compound (2b) 500 + 50  100 Present fused heterocyclic compound 17 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 17 + diamide compound (2c) 500 + 50  100 Present fused heterocyclic compound 18 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 18 + chlorantraniliprole 500 + 500  100 Present fused heterocyclic compound 18 + chlorantraniliprole 500 + 50  100 Present fused heterocyclic compound 18 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 18 + diamide compound (2b) 500 + 500  100 Present fused heterocyclic compound 18 + diamide compound (2b) 500 + 50  100 Present fused heterocyclic compound 18 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 18 + diamide compound (2c) 500 + 50  100 Untreated group — 0

TABLE 52 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 19 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 19 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 19 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 19 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 19 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 19 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 19 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 19 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 20 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 20 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 20 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 20 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 20 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 20 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 20 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 20 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 22 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 22 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 22 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 22 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 22 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 22 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 22 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 22 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 25 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 25 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 25 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 25 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 25 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 25 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 25 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 25 + diamide compound (2c) 500 + 50 100 Untreated group — 0

TABLE 53 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 27 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 27 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 27 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 27 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 27 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 27 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 27 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 27 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 28 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 28 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 28 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 28 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 28 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 28 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 28 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 28 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 29 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 29 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 29 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 29 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 29 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 29 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 29 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 29 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 34 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 34 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 34 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 34 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 34 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 34 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 34 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 34 + diamide compound (2c) 500 + 50 100 Untreated group — 0

TABLE 54 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 36 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 36 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 36 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 36 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 36 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 36 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 36 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 36 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 39 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 39 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 39 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 39 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 39 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 39 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 39 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 39 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 48 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 48 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 48 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 48 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 48 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 48 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 48 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 48 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 50 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 50 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 50 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 50 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 50 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 50 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 50 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 50 + diamide compound (2c) 500 + 50 100 Untreated group — 0

TABLE 55 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 53 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 53 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 53 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 53 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 53 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 53 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 53 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 53 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 71 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 71 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 71 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 71 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 71 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 71 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 71 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 71 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 72 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 72 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 72 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 72 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 72 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 72 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 72 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 72 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 74 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 74 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 74 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 74 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 74 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 74 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 74 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 74 + diamide compound (2c) 500 + 50 100 Untreated group — 0

TABLE 56 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 81 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 81 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 81 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 81 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 81 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 81 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 81 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 81 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 85 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 85 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 85 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 85 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 85 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 85 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 85 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 85 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 89 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 89 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 89 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 89 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 89 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 89 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 89 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 89 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 99 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 99 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 99 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 99 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 99 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 99 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 99 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 99 + diamide compound (2c) 500 + 50 100 Untreated group — 0

TABLE 57 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 130 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 130 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 130 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 130 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 130 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 130 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 130 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 130 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 312 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 312 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 312 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 312 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 312 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 312 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 312 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 312 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 399 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 399 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 399 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 399 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 399 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 399 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 399 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 399 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 404 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 404 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 404 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 404 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 404 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 404 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 404 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 404 + diamide compound (2c) 500 + 50 100 Untreated group — 0

TABLE 58 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 409 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 409 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 409 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 409 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 409 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 409 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 409 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 409 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 414 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 414 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 414 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 414 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 414 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 414 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 414 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 414 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 419 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 419 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 419 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 419 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 419 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 419 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 419 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 419 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 421 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 421 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 421 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 421 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 421 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 421 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 421 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 421 + diamide compound (2c) 500 + 50 100 Untreated group — 0

TABLE 59 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 423 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 423 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 423 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 423 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 423 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 423 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 423 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 423 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 443 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 443 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 443 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 443 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 443 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 443 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 443 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 443 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 444 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 444 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 444 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 444 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 444 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 444 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 444 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 444 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 445 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 445 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 445 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 445 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 445 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 445 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 445 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 445 + diamide compound (2c) 500 + 50 100 Untreated group — 0

TABLE 60 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 464 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 464 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 464 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 464 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 464 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 464 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 464 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 464 + diamide compound (2c) 500 + 50 100 Present fused heterocyclic compound 467 + chlorantraniliprole 200 + 2000 100 Present fused heterocyclic compound 467 + chlorantraniliprole 500 + 500 100 Present fused heterocyclic compound 467 + chlorantraniliprole 500 + 50 100 Present fused heterocyclic compound 467 + diamide compound (2b) 200 + 2000 100 Present fused heterocyclic compound 467 + diamide compound (2b) 500 + 500 100 Present fused heterocyclic compound 467 + diamide compound (2b) 500 + 50 100 Present fused heterocyclic compound 467 + diamide compound (2c) 200 + 2000 100 Present fused heterocyclic compound 467 + diamide compound (2c) 500 + 50 100 Untreated group — 0

Test Example 6

One (1) mg of any one of the present fused heterocyclic compounds 3, 4, 5, 9, 15, 16, 17, 18, 19, 20, 22, 25, 27, 28, 29, 34, 36, 39, 48, 50, 53, 71, 72, 74, 81, 85, 89, 99, 130, 312, 399, 404, 409, 414, 419, 421, 423, 443, 444, 445, 464 and 467 was dissolved in 10 UL of mixed solvent of xylene, dimethylformamide, and surfactant (Trade name: Sorpol 3005X, manufactured by TOHO CHEMICAL INDUSTRY CO. LTD) (4:4:1 (volume ratio)). Then, the mixture was diluted with water containing 0.02 (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give a given concentration.

Each commercial formulation of pymetrozine (Trade name: Chess Water-Dispersible Granules, manufactured by Syngenta Japan), pyridalyl (Trade name: Pleo Flowable, manufactured by Sumitomo Chemical Company, Limited) and pyriproxyfen (Trade name: Rano Emulsion, manufactured by Sumitomo Chemical Company, Limited) was diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration. Each of 1 mg of sulfoxaflo, flupyradifurone and spirotetramat (manufactured by Kanto Chemical Co., Inc.) was dissolved in 10 μL of mixed solvent of xylene, dimethylformamide, and surfactant (Trade name: Sorpol 3005X, manufactured by TOHO CHEMICAL INDUSTRY CO. LTD) (4:4:1 (volume ratio)), and was then diluted with water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by Sumitomo Chemical Company, Limited) so as to give each given concentration.

The resulting water-diluted solution of the present fused heterocyclic compound and each of the resulting water-diluted solution of pymetrozine, pyridalyl, pyriproxyfen, sulfoxaflo, flupyradifurone or spirotetramat were mixed to prepare a test solution.

Leaf disks (1.5 cm in diameter) of cabbage (Brassicae oleracea) were placed in each well of 24-well microplates (manufactured by Becton Dickinson), and 40 μL of the test solution was applied per well (hereinafter, referred to as “treated group”). An untreated group was prepared by applying 40 μL of water containing 0.02% (v/v) of the spreading agent (Trade name: Sindain, manufactured by. Sumitomo Chemical Company, Limited) only into a well.

After air drying, five diamondback moth (Plutella xylostella) (2nd instar larva) were released per well, and the wells were covered with a paper towel and then covered with a lid. At two days after the release, the number of surviving insects was counted on each well.

The mortality of the treated group and the mortality of the untreated group were calculated by the following equation 1), respectively. One replication test was performed on each group. Mortality (%)−(Total number of Tested insects−Number of Surviving insects)/Total number of Tested insects×100  Equation 1)

The results are shown in Tables 61 to 81.

TABLE 61 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 3 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 3 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 3 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 3 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 3 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 3 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 3 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 3 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 3 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 3 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 3 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 3 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 3 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 3 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 4 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 4 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 4 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 4 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 4 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 4 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 4 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 4 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 4 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 4 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 4 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 4 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 4 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 4 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 62 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 5 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 5 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 5 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 5 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 5 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 5 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 5 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 5 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 5 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 5 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 5 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 5 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 5 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 5 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 9 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 9 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 9 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 9 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 9 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 9 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 9 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 9 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 9 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 9 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 9 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 9 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 9 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 9 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 63 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 15 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 15 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 15 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 15 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 15 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 15 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 15 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 15 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 15 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 15 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 15 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 15 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 15 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 15 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 16 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 16 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 16 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 16 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 16 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 16 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 16 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 16 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 16 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 16 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 16 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 16 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 16 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 16 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 64 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 17 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 17 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 17 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 17 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 17 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 17 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 17 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 17 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 17 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 17 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 17 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 17 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 17 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 17 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 18 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 18 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 18 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 18 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 18 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 18 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 18 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 18 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 18 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 18 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 18 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 18 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 18 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 18 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 65 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 19 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 19 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 19 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 19 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 19 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 19 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 19 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 19 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 19 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 19 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 19 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 19 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 19 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 19 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 20 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 20 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 20 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 20 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 20 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 20 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 20 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 20 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 20 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 20 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 20 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 20 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 20 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 20 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 66 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 22 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 22 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 22 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 22 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 22 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 22 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 22 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 22 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 22 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 22 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 22 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 22 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 22 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 22 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 25 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 25 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 25 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 25 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 25 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 25 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 25 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 25 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 25 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 25 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 25 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 25 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 25 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 25 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 67 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 27 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 27 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 27 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 27 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 27 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 27 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 27 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 27 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 27 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 27 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 27 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 27 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 27 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 27 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 28 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 28 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 28 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 28 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 28 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 28 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 28 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 28 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 28 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 28 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 28 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 28 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 28 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 28 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 68 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 29 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 29 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 29 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 29 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 29 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 29 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 29 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 29 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 29 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 29 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 29 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 29 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 29 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 29 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 34 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 34 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 34 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 34 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 34 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 34 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 34 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 34 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 34 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 34 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 34 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 34 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 34 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 34 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 69 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 36 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 36 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 36 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 36 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 36 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 36 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 36 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 36 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 36 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 36 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 36 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 36 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 36 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 36 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 39 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 39 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 39 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 39 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 39 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 39 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 39 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 39 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 39 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 39 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 39 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 39 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 39 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 39 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 70 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 48 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 48 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 48 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 48 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 48 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 48 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 48 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 48 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 48 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 48 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 48 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 48 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 48 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 48 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 50 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 50 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 50 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 50 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 50 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 50 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 50 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 50 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 50 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 50 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 50 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 50 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 50 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 50 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 71 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 53 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 53 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 53 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 53 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 53 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 53 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 53 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 53 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 53 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 53 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 53 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 53 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 53 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 53 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 71 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 71 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 71 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 71 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 71 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 71 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 71 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 71 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 71 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 71 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 71 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 71 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 71 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 71 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 72 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 72 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 72 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 72 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 72 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 72 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 72 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 72 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 72 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 72 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 72 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 72 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 72 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 72 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 72 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 74 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 74 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 74 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 74 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 74 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 74 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 74 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 74 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 74 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 74 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 74 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 74 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 74 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 74 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 73 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 81 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 81 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 81 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 81 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 81 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 81 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 81 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 81 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 81 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 81 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 81 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 81 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 81 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 81 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 85 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 85 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 85 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 85 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 85 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 85 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 85 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 85 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 85 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 85 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 85 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 85 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 85 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 85 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 74 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 89 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 89 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 89 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 89 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 89 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 89 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 89 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 89 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 89 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 89 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 89 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 89 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 89 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 89 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 99 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 99 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 99 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 99 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 99 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 99 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 99 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 99 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 99 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 99 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 99 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 99 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 99 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 99 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 75 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 130 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 130 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 130 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 130 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 130 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 130 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 130 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 130 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 130 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 130 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 130 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 130 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 130 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 130 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 312 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 312 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 312 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 312 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 312 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 312 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 312 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 312 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 312 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 312 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 312 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 312 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 312 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 312 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 76 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 399 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 399 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 399 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 399 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 399 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 399 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 399 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 399 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 399 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 399 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 399 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 399 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 399 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 399 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 404 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 404 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 404 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 404 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 404 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 404 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 404 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 404 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 404 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 404 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 404 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 404 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 404 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 404 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 77 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 409 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 409 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 409 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 409 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 409 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 409 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 409 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 409 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 409 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 409 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 409 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 409 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 409 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 409 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 414 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 414 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 414 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 414 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 414 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 414 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 414 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 414 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 414 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 414 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 414 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 414 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 414 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 414 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 78 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 419 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 419 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 419 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 419 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 419 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 419 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 419 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 419 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 419 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 419 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 419 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 419 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 419 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 419 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 421 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 421 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 421 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 421 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 421 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 421 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 421 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 421 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 421 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 421 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 421 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 421 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 421 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 421 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 79 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 423 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 423 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 423 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 423 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 423 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 423 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 423 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 423 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 423 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 423 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 423 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 423 + pyriproxyfen 500 + 50 I00 Present fused heterocyclic compound 423 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 423 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 443 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 443 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 443 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 443 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 443 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 443 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 443 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 443 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 443 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 443 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 443 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 443 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 443 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 443 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 80 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 444 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 444 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 444 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 444 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 444 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 444 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 444 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 444 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 444 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 444 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 444 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 444 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 444 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 444 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 445 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 445 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 445 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 445 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 445 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 445 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 445 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 445 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 445 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 445 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 445 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 445 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 445 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 445 + spirotetramat 500 + 50 100 Untreated group — 0

TABLE 81 Concentration Mortality Composition (ppm) (%) Present fused heterocyclic compound 464 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 464 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 464 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 464 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 464 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 464 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 464 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 464 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 464 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 464 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 464 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 464 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 464 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 464 + spirotetramat 500 + 50 100 Present fused heterocyclic compound 467 + pymetrozine 200 + 2000 100 Present fused heterocyclic compound 467 + pymetrozine 500 + 500 100 Present fused heterocyclic compound 467 + pymetrozine 500 + 50 100 Present fused heterocyclic compound 467 + sulfoxaflo 200 + 2000 100 Present fused heterocyclic compound 467 + sulfoxaflo 500 + 500 100 Present fused heterocyclic compound 467 + sulfoxaflo 500 + 50 100 Present fused heterocyclic compound 467 + flupyradifurone 200 + 2000 100 Present fused heterocyclic compound 467 + flupyradifurone 500 + 50 100 Present fused heterocyclic compound 467 + pyridalyl 200 + 2000 100 Present fused heterocyclic compound 467 + pyridalyl 500 + 50 100 Present fused heterocyclic compound 467 + pyriproxyfen 200 + 2000 100 Present fused heterocyclic compound 467 + pyriproxyfen 500 + 50 100 Present fused heterocyclic compound 467 + spirotetramat 200 + 2000 100 Present fused heterocyclic compound 467 + spirotetramat 500 + 50 100 Untreated group — 0

INDUSTRIAL APPLICABILITY

A composition for controlling pests of the present invention can control pests. 

The invention claimed is:
 1. A composition for controlling pests comprising a compound represented by the formula (1) or N-oxide thereof and at least one compound selected from the below-mentioned Group (A); the formula (1):

wherein A¹ represents —NR⁷—, an oxygen atom, or a sulfur atom; A² presents a nitrogen atom or ═CR⁸—; R¹ represents a C1-C6 alkyl group which may be substituted with one or more atoms or group selected from Group X; R², R³ and R⁴ are the same or different to each other and each independently represent a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —S(O)₂NR¹⁰R¹¹ group, a —NR¹⁰R¹¹ group, a —NR¹⁰CO₂R¹¹ group, a —NR¹⁰C(O)R¹¹ group, a —CO₂R¹⁰ group, a —C(O)R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, a —SF₅ group, a cyano group, a nitro group, a halogen atom, or a hydrogen atom; R⁵ and R⁶ are the same or different to each other and each independently represent a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —S(O)₂NR¹⁰R¹¹ group, a —NR¹⁰R¹¹ group, a —NR¹⁰CO₂R¹¹ group, a —NR¹⁰C(O)R¹¹ group, a —CO₂R¹⁰ group, a —C(O)R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, —OC(O)R¹⁰, a —SF₅ group, a cyano group, a nitro group, a halogen atom, or a hydrogen atom, wherein R⁵ and R⁶ do not represent a hydrogen atom at the same time; R⁷ represents a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group W, a —CO₂R¹⁰ group, a —C(O)R¹⁰ group, a —CH₂CO₂R¹⁰ group, a C3-C6 cycloalkyl group, or a hydrogen atom; R⁸ represents a C1-C6 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)R¹⁰ group, a cyano group, a nitro group, a halogen atom, or a hydrogen atom; R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group X or a hydrogen atom, except for a —S(O)_(m)R¹⁰ group wherein m is 1 or 2 and R¹⁰ is a hydrogen atom; m independently represents 0, 1 or 2; and n represents 0, 1 or 2; Group X comprising a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms or one or more C1-C3 alkyl groups, a cyano group, a hydroxy group, and a halogen atom; Group W comprising: a C1-C6 alkoxy group which may be substituted with one or more halogen atoms, a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms, a hydroxy group, a halogen atom, and a cyano group; at least one compound selected from the below-mentioned Group (A): group consisting of the following Sub-group A-1, A-2, A-3, A-4, A-5 and A-6: Sub-group A-1: neonicotinoid compound selected from the group consisting of imidacloprid, clothianidin thiamethoxam, dinotefuran, acetamiprid, thiacloprid and nitenpyram; Sub-group A-2: synthetic pyrethroid compound selected from the group consisting of acrinathrin, bifenthrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, deltamethrin, etofenprox, fenpropathrin, fenvalerate, esfenvalerate, flucythrinate fluvalinate, tau-fluvalinate, halfenprox, permethrin, silafluofen, tefluthrin, tralomethrin and protrifenbute; Sub-group A-3: phenylpyrazole compound selected from the group consisting of ethiprole, fipronil, acetoprole, vaniliprole, pyriprole and pyrafluprole; Sub-group A-4: macrolide compound selected from the group consisting of abamectin, emamectin, emamectin benzoate, milbemectine, doramectin and lepimectin; Sub-group A-5: diamide compound selected from the group consisting of flubendiamide and the compound represented by formula (2):

[wherein, R¹ represents a methyl group or a bromine group, R² represents a bromine atom, a chlorine atom or a cyano group, R³ represents a methyl group, a 1-cyclopropylmethyl group or a methoxycarbonylamino group, and R⁴ represents a hydrogen atom or an ethyl group] Sub-group A-6: insecticidal compound selected from the group consisting of pymetrozine, pyridalyl, pyriproxyfen, spirotetramat, sulfoxaflo and flupyradifurone.
 2. The composition for controlling pests according to claim 1, wherein in the compound represented by the formula (1) or N-oxide thereof, R¹ is a C1-C6 alkyl group which may be substituted with one or more atoms or groups selected from Group Y; R² and R⁴ are hydrogen atoms; R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom; R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a —CO₂R¹⁰ group, a —SF₅ group, or a halogen atom; R⁶ is a —OR¹⁰ group, a —NR¹⁰R¹¹ group, a —CO₂R¹⁰ group, a —C(O)NR¹⁰R¹¹ group, —OC(O)R¹⁰, a cyano group, a halogen atom, or a hydrogen atom; R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms, a —CH₂CO₂R¹⁰ group, a C3-C6 cycloalkyl group, or a hydrogen atom, R⁸ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms or a hydrogen atom, except for a —S(O)_(m)R¹⁰ group wherein m is 1 or 2 and R¹⁰ is a hydrogen atom; and Group Y comprising: a C3-C6 cycloalkyl group which may be substituted with one or more halogen atoms and a halogen atom.
 3. The composition for controlling pests according to claim 1, wherein in the compound represented by the formula (1) or N-oxide thereof, R¹ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms; R² and R⁴ are hydrogen atoms; R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom; R⁵ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —OR¹⁰ group, a —S(O)_(m)R¹⁰ group, or a halogen atom; R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom; R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms; R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; and R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms.
 4. The composition for controlling pests according to claim 1, wherein in the compound represented by the formula (1) or N-oxide thereof: R¹ is an ethyl group; R² and R⁴ are hydrogen atoms; R³ is a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR¹⁰)₃ group, a halogen atom, or a hydrogen atom; R⁵ is a C1-C3 haloalkyl group, a —OR²⁰ group, a —S(O)_(m)R²⁰ group, or a halogen atom; R⁶ is a cyano group, a —NR¹⁰R¹¹ group, a halogen atom, or a hydrogen atom; R⁷ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms; R⁸ is a —S(O)_(m)R¹⁰ group, a cyano group, a halogen atom, or a hydrogen atom; R¹⁰ and R¹¹ are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; and R²⁰ is a C1-C3 haloalkyl group.
 5. The composition for controlling pests according to claim 1, wherein in the compound represented by the formula (1) or N-oxide thereof, A¹ is —NR⁷—.
 6. The composition for controlling pests according to claim 1, wherein in the compound represented by the formula (1) or N-oxide thereof, A¹ is an oxygen atom.
 7. The composition for controlling pests according to claim 1, wherein in the compound represented by the formula (1) or N-oxide thereof, A¹ is a sulfur atom.
 8. The composition for controlling pests according to claim 1, wherein the compound represented by the formula (1) or N-oxide thereof is a compound represented by the formula (1-2) or N-oxide thereof; the formula (1-2):

wherein R^(1a) represents a C1-C3 alkyl group; A^(2a) represents a nitrogen atom or ═CR^(8a)—; R^(3a) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10a))₃ group, a halogen atom, or a hydrogen atom; R^(5a) represents a C1-C3 haloalkyl group, a —OR^(20a) group, a —S(O)_(m)R^(20a) group, or a halogen atom; R^(6a) represents a cyano group, a —NR^(10a)R^(11a) group, a halogen atom, or a hydrogen atom; R^(7a) represents a C1-C6 alkyl group which may be substituted with one or more halogen atoms; R^(8a) represents a —S(O)_(m)R^(10a) group, a cyano group, a halogen atom, or a hydrogen atom; R^(10a) and R^(11a) are the same or different to each other and each independently represent a C1-C3 alkyl group which may be substituted with one or more halogen atoms; R^(20a) represents a C1-C3 haloalkyl group; m independently represents 0, 1 or 2; and n represents 0, 1 or
 2. 9. The composition for controlling pests according to claim 1, wherein the compound represented by the formula (1) or N-oxide thereof is a compound represented by the formula (1-3) or N-oxide thereof; the formula (1-3):

wherein A^(2b) represents a nitrogen atom or ═CR^(8b)—; R^(3b) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10b))₃ group, a halogen atom, or a hydrogen atom; R^(5b) represents a C1-C3 haloalkyl group, a —OR^(20b) group, a —S(O)_(m)R^(20b) group, or a halogen atom; R^(8b) represents a —S(O)_(m)R^(10b) group, a cyano group, a halogen atom, or a hydrogen atom; R^(10b) independently represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms; R^(20b) represents a C1-C3 haloalkyl group; m independently represents 0, 1 or 2; and n represents 0, 1 or
 2. 10. The composition for controlling pests according to claim 9, wherein in the compound represented by the formula (1-3) or N-oxide thereof, R^(3b) is a halogen atom or a hydrogen atom; R^(5b) is a C1-C3 perfluoroalkyl group, a —OR^(30b) group, or a —S(O)_(m)R^(30b) group; R^(30b) is a C1-C3 perfluoroalkyl group; and R^(8b) is a halogen atom or a hydrogen atom.
 11. The composition for controlling pests according to claim 1, wherein the compound represented by the formula (1) or N-oxide thereof is a compound represented by the formula (1-4) or N-oxide thereof; the formula (1-4):

wherein A^(2c) represents a nitrogen atom or ═CR^(8c)—; R^(3c) represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms, a —C(OR^(10c))₃ group, a halogen atom, or a hydrogen atom; R^(5c) represents a C1-C3 haloalkyl group, a —OR^(20c) group, a —S(O)_(m)R^(20c) group, or a halogen atom; R^(8c) represents a —S(O)_(m)R^(10c) group, a cyano group, a halogen atom, or a hydrogen atom; R^(10c) independently represents a C1-C3 alkyl group which may be substituted with one or more halogen atoms; R^(20c) represents a C1-C3 haloalkyl group; m independently represents 0, 1 or 2; and n represents 0, 1 or
 2. 12. The composition for controlling pests according to claim 11, wherein in the compound represented by the formula (1-4) or N-oxide thereof, R^(3c) is a halogen atom or a hydrogen atom; R^(5c) is a C1-C3 perfluoroalkyl group, a —OR^(30c) group, or a —S(O)_(m)R^(30c) group, R^(30c) is a C1-C3 perfluoroalkyl group, and R^(8c) is a halogen atom or a hydrogen atom.
 13. The composition for controlling pests according to claim 1 wherein a weight ratio of the compound represented by the formula (1) to at least one compound selected from the above-mentioned Group (A) is in a range of 100:1 to 1:100.
 14. The composition for controlling pests according to claim 1 wherein a weight ratio of the compound represented by the formula (1) to at least one compound selected from the above-mentioned Group (A) is in a range of 10:1 to 1:10.
 15. The composition for controlling pests according to claim 8 wherein a weight ratio of the compound represented by the formula (1-2) to at least one compound selected from the above-mentioned Group (A) is in a range of 100:1 to 1:100.
 16. The composition for controlling pests according to claim 8 wherein a weight ratio of the compound represented by the formula (1-2) to at least one compound selected from the above-mentioned Group (A) is in a range of 10:1 to 1:10.
 17. The composition for controlling pests according to claim 9 wherein a weight ratio of the compound represented by the formula (1-3) to at least one compound selected from the above-mentioned Group (A) is in a range of 100:1 to 1:100.
 18. The composition for controlling pests according to claim 9 wherein a weight ratio of the compound represented by the formula (1-3) to at least one compound selected from the above-mentioned Group (A) is in a range of 10:1 to 1:10.
 19. The composition for controlling pests according to claim 11 wherein a weight ratio of the compound represented by the formula (1-4) to at least one compound selected from the above-mentioned Group (A) is in a range of 100:1 to 1:100.
 20. The composition for controlling pests according to claim 11 wherein a weight ratio of the compound represented by the formula (1-4) to at least one compound selected from the above-mentioned Group (A) is in a range of 10:1 to 1:10.
 21. A method for controlling pests, which comprises the step of applying an effective amount of the composition for controlling pests according to claim 1 to pests or a habitat where pests live.
 22. A method for controlling pests, which comprises the step of applying an effective amount of the composition for controlling pests according to claim 1 to plants, plant seeds, bulbs, or a soil where plants grow. 